Herein, we report the effect of synthesis temperature on the morphologies, optical and electronic properties of magnesium oxide (MgO) nanostructures. The MgO nanostructures were synthesized at different temperatures, i.e., 100 °C, 300 °C, and 600 °C by simple chemical reaction process and their morphology, particle size, optical, and electrical properties were examined by different techniques such as scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and UV-Vis. spectroscopy. The morphological investigations revealed that various morphologies of MgO nanostructures, i.e., nanoparticles, nanosheet networks, and nanoneedles were synthesized at 100 °C, 300 °C, and 600 °C. The XRD results confirmed that with increasing the synthesis temperature, the crystallinity of the synthesized nanostructures increases. Further, the dielectric properties and AC conductivity at various frequencies for MgO nanostructures were studied which revealed that the dielectric losses decrease with increase in frequency and temperature. In addition, the observed band gap decreases from 4.89 eV to 4.438 eV (100 °C to 600 °C) representing its increase in the conductivity.