Water has long been a universal agent for suppressing fires, but is not best in all cases. For example, water is typically ineffective on oil fires, and can be dangerous. Fire-fighting foams were developed for extinguishing oil fires.
In 1902, a method of extinguishing flammable liquid fires by blanketing them with foam was introduced by Russian engineer and chemist Aleksandr Loran. Loran was a teacher in a school in Baku, the center of the Russian oil industry at that time. Impressed by large, difficult-to-extinguish oil fires that he had seen there, Loran tried to find a liquid substance that could deal effectively with them. He invented fire-fighting foam, which was successfully tested in experiments in 1902 and 1903. In 1904 Loran patented his invention, and developed the first foam extinguisher the same year.
The original foam was a mixture of two powders and water produced in a foam generator. It was called chemical foam because of the chemical action to create it. In general, the powders used were sodium bicarbonate and aluminium sulfate, with small amounts of saponin or liquorice added to stabilise the bubbles. Hand-held foam extinguishers used the same two chemicals in solution. To actuate the extinguisher, a seal was broken and the unit inverted, allowing the liquids to mix and react. Chemical foam is a stable solution of small bubbles containing carbon dioxide with lower density than oil or water, and exhibits persistence for covering flat surfaces. Because it is lighter than the burning liquid, it flows freely over the liquid surface and extinguishes the fire by a smothering (removal/prevention of oxygen) action. Chemical foam is considered obsolete today because of the many containers of powder required, even for small fires.
In the 1940s, Percy Lavon Julian developed an improved type of foam called Aerofoam. Using mechanical action, a liquid protein-based concentrate, made from soy protein, was mixed with water in either a proportioner or an aerating nozzle to form air bubbles with the free-flowing action. Its expansion ratio and ease of handling made it popular. Protein foam is easily contaminated by some flammable liquids, so care should be used so that the foam is applied only above the burning liquid. Protein foam has slow knockdown characteristics, but it is economical for post-fire security.
In the early 1950s, high-expansion foam was conceived by Herbert Eisner in England at the Safety in Mines Research Establishment (now the Health & Safety Laboratory) to fight coal mine fires. Will B. Jamison, a Pennsylvania Mining Engineer, read about the proposed foam in 1952, requested more information about the idea. He proceeded to work with the US Bureau of Mines on the idea, testing 400 formulas until a suitable compound was found. In 1964, Walter Kidde & Company (now Kidde) bought the patents for high expansion foam.
In the 1960s, National Foam, Inc. developed fluoroprotein foam. Its active agent is a fluorinated surfactant that provides an oil-rejecting property to prevent contamination. In general, it is better than protein foam because its longer blanket life provides better safety when entry is required for rescue. Fluoroprotein foam has fast knockdown characteristics and it can also be used together with dry chemicals that destroy protein foam.
In the mid-1960s, the US Navy developed aqueous film-forming foam (AFFF). This synthetic foam has a low viscosity and spreads rapidly across the surface of most hydrocarbon fuels. A water film forms beneath the foam, which cools the liquid fuel, stopping the formation of flammable vapors. This provides dramatic fire knockdown, an important factor in crash rescue firefighting.
In the early 1970s, National Foam, Inc. invented alcohol-resistant AFFF technology. AR-AFFF is a synthetic foam developed for both hydrocarbon and polar-solvent materials. Polar solvents are combustible liquids that destroy conventional fire-fighting foam. These solvents extract the water contained in the foam, breaking down the foam blanket. Hence, these fuels require an alcohol- or polar-solvent-resistant foam. Alcohol-resistant foam must be bounced off of a surface and allowed to flow down and over the liquid to form its membrane, compared to standard AFFF that can be sprayed directly onto the fire.
In 1993, Pyrocool Technologies Inc. acquired the patent rights to a wetting agent with superior cooling properties that is effective on Class A, Class B, Class D as well as pressurized and 3-dimensional fires involving both hydro carbon based fuels and polar solvents such as alcohol and ethanol.  The wetting agent is marketed under the name of Pyrocool.  Pyrocool Technologies Inc. was awarded the 1998 Presidential Green Chemistry Award by the USEPA. Carol Browner, the USEPA Administrator in 1998, described Pyrocool as the "Technology for the Third Millennium: The Development and Commercial Introduction of an Environmentally Responsible Fire Extinguishment and Cooling Agent". A dispute with the manufacturer, Baums Castorine, resulted in Baums rebranding this formula under the name Novacool UEF and has been selling this product under that name since 2008.
In 2002, BIOEX a French manufacturer of firefighting foam, pioneer in environmentally friendly foams, launched the first fluorine-free foam (ECOPOL) into the market. The foam concentrate is highly efficient on class B hydrocarbon and polar solvent fires, as well as on class A fires. Their environmental challenge has been to convince their customers to choose their new generation of green products, which are 100% fluorine free, and have proven to be effective. 
In 2010, Orchidee International of France developed the first FFHPF, the highest performing fluorine-free foam. The foam has achieved a 97% degradability rating and is currently marketed by Orchidee International under the brand name "BluFoam". The foam is used at 3% both on hydrocarbon and polar solvent fires.