In this investigation, a nanofibrous scaffold was fabricated through electrospinning of polycaprolactone (PCL) and chitosan (CS) using a novel collector to make better orientation and pore size for cell infiltration. PCL/CS nanofibers with 90-rpm collector speed and 40° angle between collector wires of the new collector have fewer diameters with better pore, size and nanofibers orientation. Mechanical properties, roughness parameters, topology, structure, hydrophilicity, and cell growing were considered for liver tissue engineering. The cell culture was done using epithelial liver mouse cells. The developed electrospun PCL/CS scaffold using novel collector would be an excellent matrix for biomedical applications especially liver tissue engineering.