Recently electrospun scaffolds show excellent response in cell adhesion, growth, and tissue healing in comparison with other techniques. So in this study, PCL and PCL/DCPD scaffolds were designed and prepared with electrospinning. The electrospun scaffolds were characterized by scanning electron microscope with X-ray elemental analysis, atomic force microcopy, differential scanning calorimetry, and contact angle analysis for optimizing the effective parameters. Fiber formation with uniform diameter and bead-free structure was obtained. Scaffold surface roughness increased from 100 nm for PCL to 440 nm for PCL/DCPD. DSC analysis showed the effects of DCPD on thermal stability of composite scaffold and the results of contact angle evaluation indicate improved hydrophilicity and ability of water absorption of PCL/DCPD composite fibers as compared to PCL fibers. MTT assay indicated lack of toxicity for human gingival fibroblast (HGF) cells after cell seeding on scaffold. Also, the composite scaffold can improve cell viability by helping their growth on its surface. So it can be concluded that by engineering the electrospinning parameters we can fabricate a PCL/DCPD composite scaffold for tissue engineering applications.