Foods differing in fat content can be distinguished through olfaction alone. The mechanisms underlying the ability of humans to discriminate between foods differing in fat content through olfaction are underexplored. In this study, beef and pork samples were prepared (raw and roasted) with low (muscle tissue; raw: 2–5%; roasted: 5%), medium (muscle tissue with lard; raw: 25–30%; roasted: 36–44%), and high (lard; raw: 40–42%; roasted: 69–70%) fat content. Olfactory triangle discrimination tests and ranking tests were performed to explore whether humans can discriminate and rank fat content of the samples through orthonasal olfaction. Headspace-Solid Phase Micro Extraction-Gas Chromatography-Mass Spectrometry (SPME-GC–MS) was used to characterize the volatile compound composition of the headspace of samples differing in fat content. Partial least-squares regression and partial least squares-discriminant analysis were performed to determine the volatile compounds that were responsible for olfactory fat content discrimination. We found that fat content in both raw and roasted samples can be distinguished through orthonasal olfaction. Perceived odor differences did not always contribute to olfactory identification of fat content. Roasted beef and pork meats with higher fat content had more abundant fatty acids, aldehydes, and ketones. Phthalic acid, isobutyl 2-ropylpentyl ester, and carbon disulfide facilitated the olfactory discrimination of fat content in raw pork and beef samples. 2-Methyl-propanal, benzaldehyde, 1-hydroxy-2-propanone, 2,3-pentanedione, 2,5-octanedione, and 2-butanone contributed to odor differences of roasted beef samples differing in fat content. We conclude that beef and pork samples differing in fat content differ in volatile compound composition of the headspace, and that these differences facilitate discrimination between samples differing in fat content based on olfaction alone.