A high internal phase emulsion based ring-opening polymerization (HIPE-ROP) of ɛ-caprolactone (CL) was conducted to fabricate macroporous scaffold in a single-step. An oil-in-oil HIPE of CL was formed using high molecular weight olefin (C10-C16) dispersed in continuous medium comprised of CL, a bifunctional cross-linking monomer bis-ɛ-caprolactone-4-yl (BCY) and catalyst stannous octoate (Sn(Oct)2). The emulsion was stabilized using nonionic surfactant, pluronic F127 and polymerization was conducted at 120 °C without any inert atmosphere for a period of 8 h. Complete monomer conversion and cross-linking was achieved and am acroporous scaffold of desired shape was obtained, having in-situ generated porosity and interconnected pores. All chemicals were purposely used without any purification and the high temperature process prevented deactivation of catalyst. The HIPE-ROP developed in this way was found to be highly feasible for conducting otherwise moisture sensitive organo-metallic catalyst based ROP. The morphology of HIPE was directly transferred to macroporous structure of the scaffold in this process where pore size was reproducibly controlled by variation in volume fraction of dispersed phase and cross-link density. The resultant macroporous scaffold showed superior compressive loading and swelling capacity. The porous scaffolds also exhibited excellent osteoblast (MG63) attachment and proliferation. HIPE-ROP based macroporous scaffold of cross-linked PCL thus developed paved a new route to create porous scaffolds of aliphatic polyesters in a single step. The method also reflected high commercial viability by potential conversion into a continuous process.