The elimination of dye pollutants from wastewater is a significant concern that has prompted extensive research into the development of highly efficient photocatalytic membranes. A novel method was proposed to prepare photocatalysis-enhanced poly(acrylonitrile-methyl acrylate) (PAN-based) membranes in this study. In detail, the blended membrane containing SiO2@TiO2 nanoparticles with a shell-core structure was first prepared via thermal-induced phase separation. The SiO2 nanoshells were dissolved, and the released TiO2 nanoparticles migrated to the membrane surface during a simple hydrolysis process, which prevents the TiO2 nanoparticles from directly contacting or interacting with the polymer matrix. The hydrogen bonds bind the exposed TiO2 with the PAN membrane surface, resulting in the formation of the TiO2@HPAN hybrid membrane. The photocatalytic efficiency of the TiO2@HPAN membrane doubled compared with that of nonhydrolyzed membranes. In the presence of UV light, the hybrid membrane can degrade 99.8% of methylene blue solution in less than 2 h, compared to only 86.1% for the blended membranes. Further, the TiO2@HPAN membrane showed excellent photocatalytic activity for cationic dyes due to electrostatic attraction. Moreover, the high-flux recovery rate and recycling stability of the TiO2@HPAN membrane lead to an excellent antifouling property. The facile preparation method proposed in this work shows extraordinary potential for the development of highly efficient selective photocatalytic materials for cationic dyes to be used in wastewater treatment applications.