Abstract In this paper, undoped and doped (Fe, Co and Fe-Co) nickel oxide (NiO) nanostructures have been synthesized using co-precipitation method. Prepared samples were characterized for the structural, compositional, morphological and optical properties using x-ray diffraction, scanning electron microscopy (SEM), Energy dispersive spectrocopy (EDS), UV-visible spectroscopy and photoluminescence spectroscopy. Structural analysis confirmed the single cubic phase formation of undoped and doped samples. Defect chemistry showed that Fe-Co co-doped NiO possesses a lower density of defects than other samples. SEM results revealed the agglomeration of particles. EDS results confirmed the presence of Ni, O, Fe and Co in the respective undoped and doped samples. Optical analysis revealed the band edge shifts with the incorporation of dopants in the NiO crystal lattice confirmed the variation of band gap energy. Emission peaks were observed in the UV and visible regions. The Incorporation of dopants in the crystal lattice causes variation of emission centers. Surface oxygen vacancies and imperfections significantly impact the emission characteristics of NiO. Variable spectral response of NiO with dopant incorporation has potential for optoelectronic applications.