A composite material poly(AA-DVB)@TiO2, which exhibits high photocatalytic activity, was prepared using poly(AA-DVB) containing the electron-withdrawing group by a sol-gel method without calcination. The physicochemical properties of poly(AA-DVB)@TiO2 were characterized by XRD, SEM, TEM, BET, EDS, and XPS. Photocatalytic measurements were conducted using a xenon lamp with the aim of analyzing the degradation of methyl blue (MB) and methyl orange (MO) solutions. For the photodegradation of MB and MO, poly(AA-DVB)@TiO2 exhibits photocatalytic activity significantly higher than that of TiO2 solid nanocrystals. After five cycle experiments, poly(AA-DVB)@TiO2 exhibits better efficiency. The experiments confirmed that the aromatic rings and carboxyl groups, which lead to the negative conjugation effect, synergistic effect, and higher separation efficiency of photogenerated electrons and holes, can greatly improve the photocatalytic activity of TiO2. Light capture results indicate that the main catalytic factor in poly(AA-DVB)@TiO2 as the photocatalyst is the holes. Further, the high surface area and pore also improve the photocatalytic efficiency.