This study carried out a comparison between cement grouting and chemical grouting, using epoxy and polyurethane, with respect to their effects on the shear behavior of joints. Joint replicas, with three different grades of surface roughness, were molded and grouted by means of cement and epoxy grouts of various mixtures. To investigate their shear behavior, samples were subjected to direct shear tests under constant normal load (CNL) condition. According to the results obtained, grouting improves the overall shear strength of the rock joints. All the grouted samples yielded higher maximum and residual shear strength in comparison with the non-grouted joint. Grouting resulted in an improvement in the cohesion of all the samples. However, a fall in friction angle by 5.26◦ in the sample with JRC of nine was observed, yet it was reduced by 2.36◦ and 3.26◦ for joints with JRC of 14 and 19, respectively. Cement grouts were found to have a more brittle behavior, whereas the chemical grouts were more ductile. Higher amounts of cement used in the grout mixture do not provide as much cohesion and only increase the brittleness of the grout. As a result of being more brittle, cement grout breaks into small pieces and joint planes are in better contact during shearing; consequently, there would be less of a fall in friction angle as opposed to epoxy grout whose ductile characteristic prevents grout chipping; therefore, joint planes are not in contact and a greater fall in the friction angle occurs. There was no noticeable change in the cohesion of the larger grouted joints. However, the friction angle of both natural and grouted joints increased in the larger joint. This can be related to the distribution of random peaks and valleys on the joint surface, which increases with the joint size.