A series of niobium catalysts for the selective epoxidation was synthesised by post-synthesis modification of a commercial silica, starting from niobocene dichloride through solventless organometallic precursor dry impregnation (OM-DI) or conventional liquid-phase grafting technique. OM-DI showed to be cheaper, more versatile, less time-consuming and avoided the use of environmentally unfriendly chlorinated solvents. Nb-SiO2 catalysts displayed an excellent performance in the epoxidation of limonene, using aqueous hydrogen peroxide as oxidant. Niobium-silica catalysts were obtained via OM-DI for the first time in this occasion. They showed conversions up to 78% and chemoselectivity to epoxide of 98%. An unexpected regioselectivity to exocyclic epoxide was also observed. (c) 2012 Elsevier Inc. All rights reserved.