Abstract Tricaproin was used as model system to study thermal decomposition of simple triglycerides. The tricaproin samples were pyrolyzed under three different conditions: at 250 C for 1 hr, 270 C for 1 hr and 270 C for 15 hr. Hydrocarbons, acrolein, methyl hexanoate, hexanal, hexanoic acid, 6‐undecanone, 2‐oxoheptyl hexanoate, propanediol dicaproate, propenediol dicaproate, oxopropanediol dicaproate and dicaproin were identified. Mechanisms involving both free radical and nonfree radical reactions were proposed for the formation of these compounds.