Three new CuPp-TiO2 composite materials were prepared by impregnating copper(II) porphyrin with different peripheral substituent (-OH, -COOC2H5, and -COOH) onto the surface of polycrystalline TiO2 at room temperature and characterized by SEM, energy-dispersive X-ray spectrometry, X-ray diffraction, FT-IR, UV-Vis DRS, and photoluminescence. The effects of metalloporphyrins on the surface of TiO2 have been detected by the photodegradation of 4-nitrophenol (4-NP) and rhodamine B (RhB). The loading of metalloporphyrins onto TiO2 results in strong visible light absorption by the composite and, more importantly, a 1.47-2.47 times increase in visible light photocatalytic activity in the degradation of RhB. The metalloporphyrins dispersed on the TiO2 surface can act as a small-band-gap semiconductor to absorb visible light, giving rise to electron-hole separation. What's more, these CuPp-TiO2 with different peripheral substituent (-OH, -COOC2H5, and -COOH) in meso-sites of porphyrin ring displayed different catalytic activities in the degradation of 4-NP and RhB, the CuPp containing -OH and -COOH showed better catalytic activity due to their strong interaction with TiO2. A possible mechanism of these higher photocatalytic efficiencies was proposed based on the relative experiments.