Electrospinning is a desired method to produce ultrathin fibers for tissue engineering. In order to mimic the nanofibrous structure of the extracellular matrix (ECM) poly(propylene carbonate) ultrathin fibers were electrospun using N,N-dimethyl acetamide as solvent. Cationic surfactant, cetyl trimethyl ammonium bromide, was found to aid in the formation of beadless fibers of poly(propylene carbonate). Electrospinning parameters viz. concentration of polymer and that of the surfactant used as an additive, flow rate, electrostatic field, and effect of inner diameter of the needle were investigated and optimized. Scanning electron microscopy showed porous scaffold and fibers of diameter ranging from nano- to submicron range. FTIR spectroscopy and thermal analysis of the obtained fibers ensured the complete evaporation of solvent and optimal thermal stability of fibers for tissue engineering applications. The prepared fibers possess Young's modulus of 10.19 and 26.39?GPa with the tensile strengths of 22.11 and 21.29?MPa under dry and wet conditions, respectively. The fiber mat was measured to have a porosity of 48% and exhibited competent water retention capacity of 64%. Furthermore the scaffold was found to support the adhesion of mouse NIH 3T3 fibroblasts proving its mettle as a potential scaffold for tissue engineering applications.