The penetration of external stimuli (microorganisms, ions, etc.) following to the pore is the key reason for the deterioration of cement and concrete structures. Although the traditional methods such as improving the chemical composition of cement and concrete materials can delay the erosion rate, the inevitable pore structure still makes its deterioration a challenge. Based on this, we reported a protective coating for cementitious materials based on phenol and Ti3C2MXene-modified polyacrylate (MXene-PG/PA). The introduction of phenols enhanced the waterproof properties of polyacrylate by increasing the interaction among molecular chains. Moreover, the introduction of Ti3C2MXene also endows the MXene-PG/PA coating with good light-induced antimicrobial properties. Beneficial to these designs, the MXene-PG/PA coating exhibited good waterproof properties (the water absorption ratio in seawater decreased by 58.2%) and antimicrobial properties (inhibition ofE. coliandS. epidermidisactivity under light). These results not only confirm that the MXene-PG/PA coating is a potential candidate of protective coating for cement-based materials, but also provide a new strategy for the design of multifunctional protective coatings.