We demonstrated a water-resistant PEDOT:PSS HTL by incorporating a photo-crosslinking agent into a PEDOT:PSS film. A crosslinking system was successfully formed inside the PEDOT:PSS film by simple and fast photo-polymerization of PCDSA monomers. Combination of the crosslinking system and MeOH surface treatment simultaneously improved the device efficiency and stability of both perovskite and polymer solar cells. The crosslinking system inside PEDOT:PSS changed its intrinsic water-soluble characteristic into a water-resistant property, thus preventing water penetration into the PEDOT:PSS film. In addition, MeOH treatment improved the surface conductivity and reduced the surface roughness of the PEDOT:PSS film by removing surface residues of PDAs and insulating PSS parts.