As a low-cost additive to anaerobic digestion (AD), magnetic biochar (MBC) can act as an electron conductor to promote electron transfer to enhance biogas production performance in the AD process of sewage sludge and has thus attracted much attention in research and industrial applications. In the present work, Camellia oleifera shell (COS) was used to produce MBC as an additive for mesophilic AD of sewage sludge, in order to explore the effect of MBC on the mesophilic AD process and its enhancement mechanism. Analysis by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectrometry (FTIR), and X-ray diffraction (XRD) further confirmed that biochar was successfully magnetized. The yield of biogas from sewage sludge was enhanced by 14.68–39.24% with the addition of MBC, and the removal efficiency of total solid (TS), volatile solids (VS), and soluble chemical oxygen demand (sCOD) were 28.99–46.13%, 32.22–48.62%, and 84.18–86.71%, respectively. According to the Modified Gompertz Model and Cone Model, the optimum dosage of MBC was 20 mg/g TS. The maximum methane production rate (Rm) was 15.58% higher than that of the control reactor, while the lag-phase (λ) was 43.78% shorter than the control group. The concentration of soluble Fe2+ and Fe3+ were also detected in this study to analyze the function of MBC for improving biogas production performance from sewage sludge. The biogas production was increased when soluble Fe3+ was reduced to soluble Fe2+. Overall, the MBC was beneficial to the resource utilization of COS and showed a good prospect for improving mesophilic AD performance.