Homopolymers and block copolymers of higher epoxides (butene oxide and hexene oxide) are synthesized using 1-alkanols and polyethylene glycol monomethyl ether (PEG-MME) 1100 as initiators by anionic ring opening polymerization in bulk. Most of the samples were synthesized with controlled microwave heating in sealed vessels. Tri- and tetrablock copolymers with different repeat units in the individual blocks are synthesized by living polymerization with addition of the next monomer after complete consumption of the previous one. The products thus obtained are characterized using size exclusion chromatography (SEC), liquid chromatography under critical conditions (LCCC) and liquid adsorption chromatography (LAC).