With the aim of exploring possible application of the concept of blend compatibilisation into the field of biodegradable membranes, a study of the influence of random copolymer poly(D,L-lactide-co-epsilon-caprolactone) on the properties of corresponding homopolymer blends has been conducted. Blends of plain homopolymers and blends containing 5 and 10 wt% of a copolymer of suitable composition have been prepared in the melt and characterised for their molecular interactions using thermal, dynamic-mechanical, mechanical (tensile tests) and morphological analyses. The blends are characterised by a good dispersion of the poly-epsilon-caprolactone (PCL) minor phase into the poly(D,L-lactic acid) (PDLLA) matrix and better mechanical properties compared to plain PDLLA, and such characteristics further improve when adding the copolymer. Microporous blend membranes consisting of PDLLA and PCL were then prepared by a phase inversion method and characterised by scanning electron microscopy. The addition of compatibilising agent led to a highly homogeneous structure, while in absence of compatibiliser a clear phase separation occurred.