Titanium dioxide (TiO 2 ) and TiO 2 /copper (denoted as TC) composite were prepared via hydrothermal process. In the meantime, divinylbenzene (DVB) and bismaleimide (BMI) monomers were allowed to participate in in-situ radical polymerization in the presence of azobisisobutyronitrile (AIBN) initiator to afford porous polymers (abridged as PP). The as-obtained PP were mixed together with tetrabutyl titanate (TBT) and CuSO 4 ·5H 2 O in vacuum to obtain PP/TC composite (denoted as PPTC) containing incorporated TC composite in the pores of PP. The as-prepared TiO 2 , TC, and PPTC were characterized by transmission electron microscopy, scanning electron microscopy, X-ray diffraction, fluorescence spectrometry, and electron spin resonance spectrometry, and so on. Furthermore, their photocatalytic activity for the degradation of N,N-dimethylformamide, methyl orange, phenol, and methylene blue under the irradiation of simulated sunlight (Xe lamp light) and natural sunlight were investigated. Findings indicated that, whether under simulated sunlight or nature sunlight irradiation, PPTC exhibited much better photocatalytic performance than TiO 2 and TC for the degradation of the tested organic pollutants. Particularly, it allowed N,N-dimethylformamide (DMF) to be degraded by a rate of 73.7% under simulated sunlight irradiation and it retained photocatalytic activity even after six cycles of reuse, exhibiting promising potential for the removal of organic pollutants in wastewater (including industrial water, aquaculture wastewater, and domestic sewage). The desired photocatalytic performance of the as-prepared PPTC is attributed to two aspects. Namely, the incorporation of Cu 2+ into the fine structure of TiO 2 contributes to increasing photocatalyst activity and producing more free radical while the embedding of TC composite into the PP pores improves to the contact area between the photocatalyst and organic pollutants, and both are beneficial for improving the adsorption capacity and activity of the photocatalyst, thereby enhancing the degradation of the organic pollutants.