The first reported metallic glass was an alloy (AuSi) produced at Caltech by W. Klement (Jr.), Willens and Duwez in 1960. This and other early glass-forming alloys had to be cooled extremely rapidly (on the order of one megakelvin per second, 10 K/s) to avoid crystallization. An important consequence of this was that metallic glasses could only be produced in a limited number of forms (typically ribbons, foils, or wires) in which one dimension was small so that heat could be extracted quickly enough to achieve the necessary cooling rate. As a result, metallic glass specimens (with a few exceptions) were limited to thicknesses of less than one hundred micrometers.
In 1969, an alloy of 77.5% palladium, 6% copper, and 16.5% silicon was found to have critical cooling rate between 100 and 1000 K/s.
In 1976, H. Liebermann and C. Graham developed a new method of manufacturing thin ribbons of amorphous metal on a supercooled fast-spinning wheel. This was an alloy of iron, nickel, and boron. The material, known as Metglas, was commercialized in the early 1980s and is used for low-loss power distribution transformers (amorphous metal transformer). Metglas-2605 is composed of 80% iron and 20% boron, has a Curie temperature of  and a room temperature saturation magnetization of 1.56 teslas.
In the early 1980s, glassy ingots with a diameter of  were produced from the alloy of 55% palladium, 22.5% lead, and 22.5% antimony, by surface etching followed with heating-cooling cycles. Using boron oxide flux, the achievable thickness was increased to a centimeter.
In 1982, a study on amorphous metal structural relaxation indicated a relationship between the specific heat and temperature of (FeNi)P.  As the material was heated up, the properties developed a negative relationship starting at 375 K, which was due to the change in relaxed amorphous states.  When the material was annealed for periods from 1 to 48 hours , the properties developed a positive relationship starting at 475 K for all annealing periods, since the annealing induced structure disappears at that temperature.  In this study, amorphous alloys demonstrated glass transition and a super cooled liquid region. Between 1988 and 1992, more studies found more glass-type alloys with glass transition and a super cooled liquid region. From those studies, bulk glass alloys were made of La, Mg, and Zr, and these alloys demonstrated plasticity even when their ribbon thickness was increased from 20 μm to 50 μm.  The plasticity was a stark difference to past amorphous metals that became brittle at those thicknesses.
In 1988, alloys of lanthanum, aluminium, and copper ore were found to be highly glass-forming. Al-based metallic glasses containing  Scandium exhibited a record-type tensile mechanical strength of about .
Before new techniques were found in 1990, bulk amorphous alloys of several millimeters in thickness were rare, except for a few exceptions, Pd-based amorphous alloys had been formed into rods with a  diameter by quenching, and spheres with a  diameter were formed by repetition flux melting with BO and quenching.
In the 1990s new alloys were developed that form glasses at cooling rates as low as one kelvin per second. These cooling rates can be achieved by simple casting into metallic molds. These "bulk" amorphous alloys can be cast into parts of up to several centimeters in thickness (the maximum thickness depending on the alloy) while retaining an amorphous structure. The best glass-forming alloys are based on zirconium and palladium, but alloys based on iron, titanium, copper, magnesium, and other metals are also known. Many amorphous alloys are formed by exploiting a phenomenon called the "confusion" effect. Such alloys contain so many different elements (often four or more) that upon cooling at sufficiently fast rates, the constituent atoms simply cannot coordinate themselves into the equilibrium crystalline state before their mobility is stopped. In this way, the random disordered state of the atoms is "locked in".
In 1992, the commercial amorphous alloy, Vitreloy 1 (41.2% Zr, 13.8% Ti, 12.5% Cu, 10% Ni, and 22.5% Be), was developed at Caltech, as a part of Department of Energy and NASA research of new aerospace materials.
By 2000, research in Tohoku University and Caltech yielded multicomponent alloys based on lanthanum, magnesium, zirconium, palladium, iron, copper, and titanium, with critical cooling rate between 1 K/s and 100 K/s, comparable to oxide glasses.
In 2004, bulk amorphous steel was successfully produced by two groups: one at Oak Ridge National Laboratory, who refers to their product as "glassy steel", and the other at the University of Virginia, calling theirs "DARVA-Glass 101". The product is non-magnetic at room temperature and significantly stronger than conventional steel, though a long research and development process remains before the introduction of the material into public or military use.
In 2018 a team at SLAC National Accelerator Laboratory, the National Institute of Standards and Technology (NIST) and Northwestern University reported the use of artificial intelligence to predict and evaluate samples of 20,000 different likely metallic glass alloys in a year. Their methods promise to speed up research and time to market for new amorphous metals alloys.