A novel generation of homogeneous catalysts for the epoxidation of geraniol, in the presence of tert-butyl hydroperoxide oxidant is reported. Oxidovanadium(IV) complexes of 3-hydroxy-4-pyrone and 3-hydroxy-4-pyridinone ligands exhibit excellent activity and selectivity towards the 2,3-epoxygeraniol product, only differing in the reaction times and turnover frequencies. The pyrone based complexes are the most efficient catalysts showing performances similar to that of the well known oxidovanadium(IV) acetylacetonate catalyst.