The thermal ring-opening polymerization of 5-benzyloxy-trimethylene carbonate (BTMC) in bulk in the absence of any catalyst resulted in high molecular weight poly(BTMC) ((M) over bar (n) = 80 300) and subsequent catalytic hydrogenolysis resulted in functional poly(5-hydroxyl-trimethylene carbonate) (PHTMC). Similar spontaneous polymerization of BTMC in the presence of PEG ((M) over bar (n) = 2 000) as a macroinitiator can provide amphiphilic block polymers. The results revealed that the thermal non-catalyst (co)polymerization of BTMC is a highly attractive preparative method because of the lack of usage of toxic initiators or catalysts. Furthermore, an evaluation of the degradation and cytotoxicity of PHTMC demonstrated enhanced degradability compared to poly(trimethylene carbonate) and similar toxicity compared to PLGA, showing PHTMC to be a promising biomaterial.