A polybenzimidazole supported Mo(VI) (PBI.Mo) catalyst has been prepared and characterised. The catalytic activities of the PBI.Mo catalyst in epoxidation of alkene with tert-butyl hydroperoxide (TBHP) as oxidant have been studied under different reaction conditions in a batch reactor. The batch experimental data provided useful information for conducting continuous experiments in a reactive distillation column (RDC).