A novel carbon nanotubes/porous-network carbon micron tubes/silk fibroin (CPS) composite film neural electrode was presented and characterized. This electrode was fabricated through assembling dispersed carbon nanotubes (CNTs) by phytic acid onto the porous silk fibroin film. Afterward, the silk fibroin around the CNTs was carbonized by laser irradiation, producing porous-network carbon microtubes with good conductivity and biological compatibility. The structure of the CPS composite film was characterized by scanning electron microscopy and Raman spectroscopy. Cyclic voltammetry, electrochemical impedance spectroscopy, and safe charge injection limit (Qinj) of the CPS electrode were also measured by the three-electrode system, and the results exhibited outstanding electrochemical properties with the achieved Qinj of 5.7 mC/cm2. This work provides a promising approach for the preparation of a long-term implanted neural electrode with high charge injection ability and good biocompatibility.