An organosoluble ammonium molybdate salt catalytically converts allylic hydroperoxides of fatty acid methyl esters with good selectivities into either their corresponding alcohols or enones depending on the reaction conditions. Whereas a gentle heating of methyl oleate hydroperoxides in toluene at 80 °C mainly provides the enone in a 83/17 ratio, presence of triethylamine at 40 °C reverses this ratio to 7/93 in favor of the alcohol. Extension of the reaction scope to other alkenes like cyclohexene, cyclooctene, α- and β-pinenes, β-citronellol, and 2-octene shows the wide potential applications of the process which lead to relevant oxygenated building blocks, especially oils as a possible alternative of castor oil.