Two kinds of niobium(V)-silica catalysts for the selective epoxidation were synthesised by post-synthesis modification of non-ordered mesoporous silica supports, starting from niobocene dichloride via solventless organometallic precursor dry impregnation or conventional liquid-phase grafting technique. Grafted Nb/SiO2 solids were used as catalysts, in the presence of aqueous H2O2, for the epoxidation of unsaturated cyclic and terpenic compounds of interest for fine and specialty chemistry, in particular: cyclohexene, 1-methylcyclohexene, limonene, carveol, alpha-terpineol, isopulegol, carvotanacetol, carvone, as well as squalene and isopulegyl acetate. These catalysts showed high yields (up to 73%) and excellent chemoselectivities to the desired epoxides (up to 98%), also in short reaction times (down to 1 h). (C) 2014 Elsevier B.V. All rights reserved.