Nanoparticles (NPs) of Cu1-xNixFe2O4 (0 ≤ x ≤ 0.5) have been facilely prepared via combustion through microwave technique. X-ray diffraction outcomes confirmed single-cubic phase synthesis of titled material and mean crystallites size and lattice constants were calculated in range of 19.37–22.69 nm and 8.319–8.248 Å, respectively. The XPS study confirms the chemical elements and oxidations states of Cu0.6Ni0.4Fe2O4 NPs. The high-resolutionSEM study reveals spherical NPs with agglomeration and composition of elements in Cu1-xNixFe2O4 (0 ≤ x ≤ 0.5) was confirmed through EDX study. The Kubelka-Munk model was employed to determine the energy gap of Cu1-xNixFe2O4 NPs and noticed to vary from 2.30 to 2.06 eV. Photoluminescence spectra study explained the rate of recombination of electron and hole pairs. The detailed magnetic study was carried out and magnetization of remanence (Mr), coercivity (Hc) & saturation (Ms) values were estimated through recording the hysteresis plots. The magnetic Mr & Ms values are noticed to be enhanced from 5.21 to 11.02 emu/g &17.37–31.37 emu/g with Ni content. Furthermore, the Cu1-xNixFe2O4 (0 ≤ x ≤ 0.5) NPs were studied by means of visible light induced RhB dye degradation and investigates major active species and a probable mechanism for degradation has been conferred. The photocatalytic activity of CuFe2O4 NPs has been improved via Ni doping. Photoluminescence spectra showed the rate of recombination of electron-hole pairs and presence of defects.