PbO/ZnO core/shell nanocomposites dispersed in PVP has been synthesized through chemical route with a thickness variation of ZnO shell. The structural, optical and electrical characterization are done and correlated with the shell thickness. PbO shows an orthorhombic structure and that of PbO/ZnO contain the hexagonal phase of ZnO. HRTEM and SEM confirm the respective products from the lattice fringe, SEAD and compositional studies. A coating over the PbO core reduces the band gap and PL intensity whereas it increases the conductance and refractive index which is attributed to the predominance of exciton leakage on shelling over surface passivation . The conductivity mechanism has been studied which is found to be of Richardson-Schottky type in the high operating voltage range. Mem-properties have been analyzed by observing the cyclic loop of I–V characteristics which reveals primarily a mem-capacitive in nature. The pinching voltage and current increases quite linearly with the increase of ZnO shell thickness that may be attributed to the effect of oxygen vacancies in the shell. These studies show that PbO/ZnO core/shell nanocomposites may be one of the promising oxide nanomaterials in future application of memcapacitive devices. • PbO/ZnO core/shells have been synthesized through chemical route. • Shelling reduces the band gap and PL intensity of core. • Whereas it increases the conductance and refractive index. • Richardson-Schottky type mechanism prevails at high operating range of voltage. • Mem-capacitive properties have been found from I–V hysteresis loops.