Through exploitation of hydrothermal synthesis, a mixture of crystals containing blue [CuMoO4(N2C12H8)]·H2O (1) and yellow ([Cu3ICl(4,4′-bipy)4][CuII(1,10-phen)2Mo8O26]) (4,4′-bipy=4,4′-bipyridine and 1,10-phen=1,10-phenanthroline) (2) were obtained. Single crystal X-ray diffraction analysis revealed that compound 1 is a new 1-D coordination polymer while compound 2 is a known metal–organic framework. The obtained crystals have been further characterized by means of powder X-ray diffraction (PXRD), FT-IR and inductive coupled plasma optical emission spectroscopy (ICP-OES). The catalytic properties of the prepared mixture were investigated in the epoxidation of some olefins and allylic alcohols using tert-butyl hydroperoxide (TBHP) or cumene hydroperoxide (CHP) as oxidants. It was found that the crystals could serve as an active and selective catalyst for the epoxidation of the olefins and allylic alcohols. The catalyst can be recovered easily and reused in the reaction without considerable decrease in activity or selectivity. Moreover, the influence of the type of oxidant and solvent on the conversion of the olefins was studied.