Understanding the potential mechanism of in-situ polymerization of acrylamide (AM) for modifying seawater cementitious materials is crucial for designing high-strength and durable marine concrete. Herein, the acrylamide (AM) in-situ polymerization was investigated for its effects on the hydration behavior, micro-morphology, and pore structure of cementitious materials mixed with seawater and freshwater through a series of elaborately designed microscopic characterization methods. The results reveal that the hydration process of cementitious materials proceeds simultaneously with in-situ polymerization. However, compared with freshwater mixtures, seawater provides a large number of metal ions and SO42- ions, which can cross-link with the generated polyacrylamide (PAM) during in-situ polymerization to form a three-dimensional network structure. The synergistic effect of the hydration, in-situ polymerization, and cross-linking processes of cementitious materials can improve the pore structure of seawater-mixed paste, enhance erosion resistance, and improve the stability and toughness of microstructure. These findings were further confirmed by comparing infrared spectroscopy results, hydration products, pore size, and micro-morphology analysis as well as flexural performance tests. This is of great significance to guide the design of novel materials in marine infrastructure.