Homopolymers and block copolymers of higher epoxides (butene oxide and hexene oxide) are synthesized using 1-alkanols and PEG-MME 1100 as initiators by anionic ring opening polymerization in bulk employing controlled microwave heating in sealed vessels. The selectivity of polymerization of higher epoxides and the effect of different reaction parameters on the formation of side products is discussed. A procedure for the generation of fairly clean homopolymers and multiblock copolymers (giving bottlebrush and cone type of structures) is developed.