In the present paper, we report a facile and rapid microwave-assisted combustion synthesis method for the preparation of pure and Ni-doped CuO nanostructures with different weight ratios (0.5, 1.0, 1.5, and 2.0 at wt% of Ni). The structure and morphology of the pure and Ni-doped CuO samples were investigated by X-ray diffraction (XRD), high resolution scanning electron microscopy (HR-SEM), energy dispersive x-ray analysis (EDX), diffuse reflectance spectroscopy (DRS), photoluminescence (PL) spectroscopy and vibrating sample magnetometry (VSM). XRD patterns refined by the Rietveld method indicated the formation of single-phase monoclinic structure and also confirmed that Ni ions are successfully doped into CuO crystal lattice by occupying Cu ionic sites. Interestingly, the morphology was found to transform substantially from nanoflowers to nanoparticles with close-packed periodic array, and then into nanocrystals with the variation of Ni content. The optical band gap estimated using DRS was found to be 3.9 eV for pure CuO and then increases up to 4.3 eV with increasing Ni content. PL spectra at room temperature showed a strong green emission band, and thereby confirmed the above results. Magnetic measurements reveal a room temperature ferromagnetism (RTFM) with an optimum value of saturation magnetization of 1.3140×10-3 emu/g for 2.0 wt% of Ni. © 2013 Elsevier Ltd.