Recently, in the field of tissue engineering, fabrication of three dimensional (3D) electrospun membrane is much emphasized. 3D scaffold fabricated from multi-layered electrospun membrane possess both the benefits of nanofibrous and microfibrous scale morphology in one scaffold. In this book, layered composite scaffolds or membranes were fabricated using blend of Polycaprolactone (PCL) /Chitosan and PCL layer-by-layer using multilayer electrospinning techniique. Characterization of membranes were conducted using several techniques. Using optimized solution concentration and processing parameters, the composite PCL/Chitosan and PCL layer-by-layer membrane were successfully fabricated. From the scanning electron micrographs, it was observed that the composite electrospun membranes produced microfibers and nanofibers morphology within single scaffold. In another part of this book, PCL was blended with Chitosan using a common solvent formic acid and acetic acid. The ratio of concentration of the polymers was varied in order to form different level of viscosity of polymeric solutions. Then the PCL/Chitosan nanofibers were fabricated via electrospinning technique.