Kinetic peculiarities of cis and trans methyl oleate formation in the course of methyl linoleate hydrogenation over Pd/MgO were studied. Liquid phase hydrogenation was carried out in temperature range of 303–323K and under hydrogen pressure within 1–10bar. Gas–liquid chromatography, IR and 13C NMR techniques were employed to characterize the reaction products. Effects of hydrogen pressure and reaction temperature on cis and trans methyl oleate formation were studied. The general kinetic scheme and reaction mechanism of methyl linoleate hydrogenation and cis–trans methyl oleate isomerization have been proposed.