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Wastewater from the textile industries contaminates the natural water and affects the aquatic environment, soil fertility and biological ecosystem through discharge of different hazardous effluents. Therefore, it is essential to remove such dissolved toxic materials from water by applying more efficient techniques. We performed a comparative study on the removal of rhodamine B (RhB) and Nile blue (NB) from water through a catalytic/photocatalytic approach while using a CuO–SiO2 based nanocomposite. The CuO–SiO2 nanocomposite was synthesized through a sol–gel process using copper nitrate dihydrate and tetraethylorthosilicate as CuO and SiO2 precursors, respectively, with ammonia solution as the precipitating agent. The synthesized nanocomposites were characterized, for their structure, morphology, crystallinity, stability, surface area, pore size and pore volume, by using a scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Brunauer–Emmett–Teller (BET) techniques. The CuO–SiO2 nanocomposite was used for potential environmental applications in the terms of its catalytic and photocatalytic activities toward the degradation of rhodamine B (RhB) and Nile blue (NB) dyes, in the presence and absence of light, while monitoring the degradation process of dyes by UV-Visible spectroscopy. The catalytic efficiency of the same composite was studied and discussed in terms of changes in the chemical structures of dyes and other experimental conditions, such as the presence and absence of light. Moreover, the composite showed 85% and 90% efficiency towards the removal of rhodamine B and Nile blue dyes respectively. Thus, the CuO–SiO2 nanocomposite showed better efficiency toward removal of Nile blue as compared to rhodamine B dye while keeping other experimental variables constant. This can be attributed to the structure–property relationships and compatibility of a catalyst with the molecular structures of dyes. [ABSTRACT FROM AUTHOR]