This study aimed to investigate the effect of poly(vinyl alcohol) (PVA) polymer on the thermal, mechanical, and surface properties on cementitious composites for sustainable development. Thermal properties of the PVA-modified cement paste, including thermal insulation and energy absorption ability, were first studied and correlated with the porosity and microstructures. The experimental results indicated that the thermal conductivity of cement paste can be greatly reduced by 42.9% with 2.0 wt % addition of PVA due to the more porous structure. However, at the same time, more thermal energy can be captured and concentrated at the surface of cement paste with the increasing amount of PVA, causing an increased thermal load and a negative effect on thermal insulating efficiency of cement paste. The contradictory effect of PVA on thermal properties of cement paste should be balanced before it is used as a foaming modifier to fabricate cementitious composites with thermal insulation. In addition, the contact angle measurement revealed that PVA can be used as an effective additive to improve the hydrophobicity of cement-based materials. Only 3.0% PVA can turn the surface nature from hydrophilicity to hydrophobicity for cement paste, which benefited to the development of self-cleaning cementitious composites. Finally, the mechanical properties of the PVA-modified cement paste, especially for the tensile strength that has been rarely reported, were investigated and correlated with its thermal and surface properties. Due to the compensative effects of irregular packing, formation of PVA films and microcracks, tensile strength of cement paste can be improved by 23.5% with a small scarifying of the compressive strength by adding 2.0% of PVA. In conclusion, the PVA-modified cement-based materials with lower thermal conductivity, hydrophobic surface nature and enhanced mechanical properties have a great potential to satisfy the high requirements in developing sustainable infrastructure.