The low flexural strength and high brittleness of cementitious materials impair their service life in building structures. In this study, we developed a new polymer-modified mortar by in situ polymerization of acrylamide (AM) monomers during the cement setting, which enhanced the flexural and durable performances of mortars. The mechanical properties, micro-and-pore structures, hydrated products, interactions between cement hydrates and polyacrylamide (PAM), and durability-related properties of the mortars were investigated comprehensively. Mortars with 5% PAM exhibited the best performance in terms of flexural strength among all the mixtures. The mechanical strength of cement pastes modified by in situ polymerization of AM monomers was significantly superior to those modified by PAM. The chemical interactions between the polymer molecules and cement hydrates together with the formation of polymer films glued the cement hydrates and polymers and resulted in an interpenetrating network structure, which strengthened the flexural strength. Reductions in porosity and calcium hydroxide content and improvement in capillary water absorption were achieved with the addition of PAM. Finally, the chloride resistance was significantly enhanced with the incorporation of PAM.