Chitosan (CS) and polycaprolactone (PCL) were added into a nerve scaffold of poly(L-lactide acid) (PLLA)/polypyrrole (PPy)-based fibre films to solve the unmatch with the nerve strength and the aseptic inflammation from PLLA.Poly (L-lactide acid)-polycaprolactone (PLLA/PCL) fibre films coated with chitosan (CS) and polypyrrole (PPy) were prepared by electrospinning of aligned PLLA/PCL fibres, electrochemical deposition of PPy nanoparticles and in situ doping of CS in PPy. PC12 cells were electrically stimulated with 100 mV for 2 hours every day via CS/PPy-PLLA/PCL fibre film to promote the neurite growth.The surface conductivity and tensile strength of CS/PPy-PLLA/PCL fibre films were 1.03 s/m and 13 MPa, respectively. CS content in fibre films was about 7.5 mg/cm , improving the pH value (reached to 5.1) of immersion solution of the fibre film at 16 days. Compared with PPy-PLLA/PCL fibre film, more and longer axons were grown out from PC12 cells cultured on CS/PPy-PLLA/PCL fibre film, indicating the positive effect of CS in fibre film on axon growth. The cell differentiation rate and neurite length on CS/PPy-PLLA/PCL fibre film reached to 38% and 75 μm, respectively. These results suggest the promotion of electrical stimulation on neurite growth and alignment.A synergistic mechanism about the promotion of CS, electrical stimulation and aligned fibres on PC12 cells differentiation, axon outgrowth was proposed. These results indicated the potential application of CS/PPy-PLLA/PCL fibre film in the field of the nerve repair and regeneration.