In this paper, the preparation of polycrystalline TiO2 samples impregnated with a modified Cu(II)-phthalocyanine (TiO2-CuPc) is reported along with an investigation on the photocatalytic behavior of this system compared with bare TiO2 (both in the anatase and rutile form) and with TiO2 samples impregnated with not functionalized commercial phthalocyanine (TiO2-CuPc) or with metal free phthalocyanine (TiO2-Pc). The photocatalytic degradation of 4-nitrophenol (4-NP) was studied as a probe reaction. The presence of modified CuPc showed to be beneficial only for TiO2 (anatase) while the commercial not functionalized CuPc also slightly for both TiO2 (anatase) and TiO2 (rutile). The metal free Pc did not show any beneficial influence on the photoactivity. A tentative explanation of the beneficial effect due to the presence of the Cu(II)-phthalocyanines both on the initial reaction rate and on the mineralization process is provided by taking into account intrinsic electronic and physico-chemical properties.