The mild oxidation of various primary amines with diluted hydrogen peroxide has been studied over vanadium silicalite molecular sieve, VS-1. The reaction leads to the corresponding oximes and imines. The nature of solvent was found to have a strong influence on the product selectivity. The use of chloroform favors the formation of nitroalkanes. Under similar conditions primary amines with no alpha-hydrogen, such as aniline, were oxidized mainly to the corresponding azoxy derivatives.