A simple method is reported for the epoxidation of hydroxyl-terminated polybutadiene (HTPB) by using in-situ generated dimethyl dioxirane (DMD) as an oxidant and Cloisite 15Aº nanoclay as a phase-transfer catalyst (PTC). In order to find the optimum reaction conditions, real time analyses of the products as well as epoxidation progress, followed by 1HNMR and FTIR techniques at various reaction times and different PTC concentrations, were done. Obtained data revealed the selectivity of DMD/ Cloisite 15Aº in predominant cis double bonds epoxidation in comparison with trans and pendant vinyl functional groups.