The improved high-performance polymer cement mortar (PCM) and glass fiber reinforced plastic (GFRP) system reinforcement was used in the research to strengthen and repair the masonry structure, so as to improve its bond stress, anchoring force, and integral performance without changing the original structure and further study the shear performance of masonry structure strengthened by the combination of the two. The optimum ratio of improved high-performance PCM was determined by analyzing the bend-press ratio of PCM test block. Improved high-performance PCM and GFRP were combined to strengthen the damaged masonry wall, and a five-piece masonry wall composed of “improved high-performance PCM+ with or without GFRP+ different original wall failure modes before reinforcement” was designed. Through diagonal loading shear test, the shear strength, vertical displacement, horizontal relative displacement, and failure models of masonry walls were obtained, and the effects of five different reinforcement methods and different materials on shear strength, stiffness, ductility, and failure modes of masonry walls were studied. The results show that compared with the unreinforced original wall, the shear strength of the masonry wall reinforced with the improved O4PCM is 43.5% higher, and its stiffness is also greatly improved, but the failure mode is still brittle failure; the shear strength of masonry walls strengthened by O4PCM and GFRP is 6.5% higher than that of masonry walls strengthened by O4PCM alone, and the stiffness is also increased. Its failure mode changes from brittle failure to ductile failure; with a failure mode of ductile failure, the shear strength of masonry walls strengthened by P4PCM and GFRP and that strengthened by P6PCM and GFRP are 4.8% and 12.7% higher than that strengthened by O4PCM and GFRP, respectively, and the stiffness is also increased compared with that strengthened by O4PCM and GFRP. After experimental comparison, it is the best scheme to strengthen masonry wall with improved P6PCM and GFRP.