A new heterogeneous catalyst (PVMo/Bentonite) consisting of vanadium substituted heteropolymolybdate with Keggin-type structure Na(5)[PV(2)Mo(10)O(40)]center dot 14H(2)O (PVMo) supported between silicate layers of bentonite has been synthesized by impregnation method and characterized using X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy and elemental analysis. X-ray diffraction and scanning electron microscopy analysis indicated that PVMo was finely dispersed into layers of bentonite as support. The PVMo/Bentonite used as an efficient heterogeneous catalyst for epoxidation of alkenes. Various cyclic and linear alkenes were oxidized into the corresponding epoxides in high yields and selectivity with 30% aqueous H(2)O(2). The catalyst was reused several times, without observable loss of activity and selectivity. The obtained results showed that the catalytic activity of the PVMo/Bentonite was higher than that of pure heteropolyanion (PVMo). (C) 2011 Elsevier Ltd. All rights reserved.