Colostrum from French-Alpine and Anglo-Nubian goats and Holstein cows was collected and analyzed for both total and FFA of 12 and fewer carbon atoms. Short-chain VFA were separated from long-chain fatty acids using simultaneous distillation extraction. The n-butyl esters of fatty acids were quantified by gas chromatography, and their identity was confirmed by gas chromatography-mass spectrometry. The concentration of decanoic acid was 33 and 83% less in Holstein colostrum than in colostrum from Alpine and Nubian goats, respectively. Colostrum from Nubian goats had twice as much decanoic acid as colostrum from Alpine goats. The FFA in colostrum that differed between species but not between goat breeds were octanoic and decanoic acids. These respective fatty acids were approximately two and three times greater in colostrum from goats than in colostrum from Holsteins. The quantity of decanoic acid was different between goat breeds and between animal species. The ratio of total fatty acid concentration to free-state concentration for hexanoic acid appeared to be useful for differentiating between Nubian and Alpine goat colostrum as well as between Nubian and Holstein colostrums. © 1993, American Dairy Science Association. All rights reserved.