What substances do humans consume that are caloric but neither protein, carb, nor fat?
If you go to https://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:01990L0496-20081211&amp;qid=1580028914722&amp;from=EN you will see a fairly extensive list of caloric compounds (screenshot pasted below).  This list is probably not comprehensive -- likely there are many compounds we (which includes our gut bacteria) can metabolize for calories.  Rather, it's limited to componds that are caloric and approved for use in food.  [It also doesn't include compounds that are naturally found in foods, and may be caloric, but are only present in very small quantities, e.g., nucleic acids.] 

You can see that, in addition to fat, proteins, carbohydrates, and ethanol, the table lists polyols, organic acids, salatrims, and fiber. 

Some explanation of the table may be helpful:

Polyols are artifical sweeteners. They include lactitol, maltitol, mannitol, sorbitol, xylitol, erythritol, glycerol, hydrogenated starch hydrolysates,  and isomalt. [Though note that while erythritol is a polyol, it is listed separately as non-caloric.  And while glycerol, aka glycerin or glycerine, is a sweetener, it is also used in food for other purposes.]

Organic acids include acetic acid (the main component of vinegar, other than water), as well as citric acid, ascorbic acid, and malic acid (the latter three are found in citrus fruits).  

Fiber refers to dietary fiber, which is the type of fiber we can digest completely.

Salatrims are "short and long chain acyl triglyceride molecules"; they are a type of low-calorie fat substitute.

Source:  Consolidated text: Council Directive of 24 September 1990 on nutrition labelling for foodstuffs (90/496/EEC) Select: 6 CELEX number: 01990L0496-20081211 Author: Council of the European Union Date of document: 11/12/2008