Single‐step process for production of porous scaffold based on poly(pentadecanolide) (PPDL) is reported. The scaffold is produced via in situ porosity generation during ring‐opening polymerization (ROP) of the lactone pentadecanolide (PDL) in high internal phase emulsion (HIPE) using a water soluble enzyme (Lipase TL) as catalyst. The enzyme present in dispersed aqueous phase of HIPE effectively carries out ROP of monomer present in continuous oil phase. The polymerization occurs at the interface of oil and water in HIPE and complete monomer conversion is achieved in 96 h at 40 °C. Porous scaffold having interconnected pores is obtained as the final product and formation of PPDL is confirmed by spectroscopic and thermal analysis. The process thus developed is a single‐step process to produce porous scaffolds via ROP of a lactone that can be extended to see its efficacy using monomer‐soluble organometallic catalysts and monomers other than PDL including lactones, lactides, and cyclic carbonates. A single step solvent free process to create porous scaffold of an aliphatic polyester, poly(pentadecanolide) is devised. Scaffold is developed via in situ pore formation during ring‐opening polymerization (ROP) of high internal phase emulsion (HIPE) of pentadecanolide comprising continuous phase and catalyst, Lipase TL, present in dispersed aqueous phase. HIPE‐ROP may further be extended for fabrication of scaffolds based on other lactones and lactides.