Ti electrodes were directly deposited at different positions on diamond-like carbon (DLC) films to form horizontal and longitudinal electric fields on their surfaces. The ID/IG ratio increased with the sp3 content in the membrane when the DLC film was laser-irradiated and the electric field intensity was 0 V/cm. The bias electric field intensity increased from 0 to 1000 V/cm, and the corresponding laser-induced damage threshold (LIDT) increased. The three-dimensional damage morphology of the DLC film with two different electrode structures was observed when the electric field intensity was 220 V/cm. Two types of electrode structures were observed in the Raman spectra under an electric field intensity of 110 V/cm and laser energy densities of 0 and 1.56 J/cm2. Results showed that the horizontal bias field had a more obvious influence than the longitudinal electric field on the decrease of the sp3–sp2 hybridization, preventing the formation of sp2 clusters, thereby slowing down the graphitization process of DLC. Applying the bias field to the DLC film could slow down the DLC film graphitization process and improve the LIDT of the DLC film.