Tissue engineering is an interdisciplinary field that applies the principles of engineering and life sciences towards the tissue development. Scaffolds can provide physical support and carry growth factors to the target cells. In this study, multi-layered composite scaffolds or membranes were fabricated using poly (lactic acid) PLA and by blending of synthetic polycaprolactone (PCL) and natural Chitosan layer-by-layer with a multilayer electrospinning technique. Scanning Electron Microscopy (SEM), water contact angle measurement (WCA) and water uptake were measured to characterize the multilayered scaffolds. Using optimized solution concentrations and processing parameters, the composite PLA and PCL/Chitosan was successfully fabricated layer-by-layer. It was found that the composite microfibrous membranes were homogenous. No beads were observed in the microfibers of the membranes. The composite layer-by layer membrane had enhanced wettability and water uptake properties than single layered membranes.