To improve the production rate of methane, powder-activated carbon (PAC), granule activated carbon (GAC), titanium dioxide-anatase (TiO2), and synthesized zeolite (permutit) were added in the co-digestion process. The co-substrates were corn stover (CS) and pig manure (PM) mixed in the ratio of 1:2 (w/w). The kinetic analysis model and ADM1da model were applied to obtain the kinetic parameters of the process. Besides, the heat flow analysis of the co-digestion process was determined using isothermal microcalorimetry. The addition of the PAC, GAC, TiO2, and synthesized zeolite improved the methane cumulative yield by 40.12, 31.25, 31.17, and 43.74% respectively, as compared with the control reactor. The kinetic analysis and ADM1da model results indicated that the overall rate constant of the co-digestion process increased by 1.5 times averagely because of the effect of these materials. It was also observed that much higher heat energy released from the experimental sample compared with the control reactor, which indicated that the improvement of the metabolic process of the AcoD system. The addition of TiO2-anatase improved methane production by 31.17%, which could be a promising method to improve the biomethane in a large-scale due to its availability and accessibility.