In the present study, highly aligned poly(-caprolactone) fibrous network produced by centrifugal spinning method was used as base substrate for electrophoretic deposition of chitosan. Two major parameters, namely the material and process parameters were varied to study its effect on add on % of chitosan in the matrices. It was found that the molecular weight and pH of the acidic chitosan solution widely influence the amount of deposition and pattern of deposition. The use of ultrasonic radiation in the electrophoretic deposition cell led to matrices with rough topography. In electrophoretic deposition process, the inherent gas bubbles formation results in formation of porous chitosan structure on the surface of centrifugal spun matrices making it suitable for biomedical applications.