Nanostructured NiO and Li-ion doped NiO have been synthesized via a facile microwave technique and simulated using the first principle method. The effects of microwaves on the morphology of the nanostructures have been studied by Field Emission Spectroscopy. X-ray diffraction studies confirm the nanosize of the particles and favoured orientations along the (111), (200) and (220) planes revealing the cubic structure. The optical band gap decreases from 3.3 eV (pure NiO) to 3.17 eV (NiO doped with 1% Li). Further, computational simulations have been performed to understand the optical behaviour of the synthesized nanoparticles. The optical properties of the doped materials exhibit violet, blue and green emissions, as evaluated using photoluminescence (PL) spectroscopy. In the presence of Li-ions, NiO nanoparticles exhibit enhanced electrical capacities and better cyclability. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) results show that with 1% Li as dopant, there is a marked improvement in the reversibility and the conductance value of NiO. The results are encouraging as the synthesized nanoparticles stand a better chance of being used as an active material for electrochromic, electro-optic and supercapacitor applications.