The present invention provides a single step, solvent free process for generation of three-dimensional porous scaffolds via in-situ porosity generation during polymerization involving homo-polymerization or cross-linking. The threedimensional scaffolds developed are comprised of aliphatic polyesters or aliphatic carbonates using lactones, lactides or cyclic carbonates as monomers and organometallic compounds as catalysts for polymerization and therefore the mode of polymerization or cross-linking developed is based on ring-opening polymerization. The purity of the monomers or catalyst is selected over a wide range to suit the applicability of the process at commercial level. The main advantages of the process are that use of organic solvents can be avoided in making three-dimensional porous scaffolds and the process is applicable to not only homo-polymers but also cross-linked polymers.