Biodegradable diblock and triblock copolymers and blends were prepared, consisting of poly(L-lactic acid) and an aromatic/aliphatic polyester mimicking polyethylene phthalate. As poly(2-(2-hydroxyethoxy)benzoate) possesses unique degradability and thermal properties, these novel block copolymers were explored through thermal analysis, UV-Vis spectroscopy, X-ray diffraction and comparative enzymatic and catalytic degradation. Poly(L-lactic acid), the product of ring opening polymerization of L-lactide by an aluminium salen catalyst, was used as a macroinitiator in the ring opening polymerization of 2,3-dihydro-5H-1,4-benzodioxepin-5-one to afford target diblock and triblock copolymers. Copolymerization dramatically improved the thermal and optical properties of poly(2-(2hydroxyethoxy)benzoate), especially in comparison to polymer blends which favored non-interacting phases that worsened properties. The chemical and enzymatic degradation profiles of the copolymers were studied by depolymerizing with the aforementioned aluminium salen catalyst and degrading with proteinase K.