AbstractBased on X‐ray diffraction and Raman spectroscopy studies of trimyristin, a structure of triglycerides in the liquid state is proposed. The order in the melt is quite constant, even if the temperature is raised as much as 40° C above the melting point. The homologue series of simple triglycerides, together with 1‐monomyristin and 1,2‐dimyristin have been studied with the same techniques. The order of different segment in the hydrocarbon chains varies when different chain length, i. e. a long chain is more disordered at the methyl endgroup plane compared with a short one. The crystallization of triglycerides is also discussed based on diffraction pattern versus temperature studies. Due to different cooling rates and different chain length a melt can crystallize not only in α but directly in