Extracellular matrix (ECM) components play a critical role in regulating cell behaviors. Interactions between ECM components and cells are important in various biological processes, including cell attachment, survival, morphogenesis, spreading, proliferation, and gene expression. In this study the in vitro responses of human induced pluripotent stem cells (hiPSCs) on polycaprolactone (PCL) electrospun nanofibrous scaffold were reported in comparison with those of the cells on corresponding solution-cast film scaffold. Our results demonstrated that the nanofibrous scaffold showed better support for the attachment and proliferation of hiPSCs than their corresponding film scaffold. Consequently, we emphasize that hiPSCs can sense the physical properties and chemical composition of the materials and regulate their behaviors accordingly.