This study deals with the immobilization of mixtures of two semiconductor oxides CuO and TiO2 on fibrous palygorskite clay mineral in order to evaluate their photocatalytic activity for removing Orange G dye as model pollutant from aqueous solutions. The elaboration of CuO–TiO2/Palygorskite nanocomposites was carried out by impregnation with Cu2+ of before hand synthesized TiO2 supported palygorskite (Pal) followed by air annealing for 5 h at 550 °C. In the composite materials, different CuO to CuO + TiO2 molar ratios were used in order to obtain a CuO content in the range 13–30 mol.%. XRD, SEM and TEM equipped with elemental EDS analysis are concordant for showing the crystallization of anatase TiO2 along with CuO whose average size of nanoparticles (NPs) are in the range 6 to 20 nm as determined by TEM. By increasing the CuO content the average size of this oxide remains constant at about 10 nm while that of TiO2 NPs is slightly decreasing from 8.4 to 5.1 nm. Both oxide NPs were successfully attached on palygorskite fibers where they form CuO–TiO2 heterojunctions (grain boundaries like). The CuO–TiO2/Pal supported photocatalyst containing 23% of CuO was found to be the most photoactive material but itremained less active than TiO2/Palygorskite supported photocatalyst. The photocatalytic activity of the mixed nanocomposites is not readily correlated with only one of their main features as CuO content or the average crystallite size of functional oxides indicating that if there are synergistic effects there are also antagonistic effects in particular for high CuO contents.