Studies on manoeuvring the optoelectronic characteristics of a semiconducting nanostructure are of recent Specific interest for a wide range of photonic applications. In this regard, the optical and electrical characteristics of ZnO nanostructures have been tuned and studied systematically using Gd ions. The structural and morphological characteristics of the solution processed ZnGdO nanostructures were studied in detail using the results of X-ray diffraction and microscopic measurements. The absorption band edge in ZnO was noted to shift towards the lower wavelength values on Gd substitution, suggesting an increase in its energy band gap. The blue emissivity from ZnO complexes was also noted to improve as a function of Gd composition in ZnO. The potential of ZnGdO nanostructures for optoelectronic functions was evaluated by fabricating heterojunction diodes based on n-ZnGdO/p-Si. The diode characteristics revealed an improved electrical conductivity and rectifying behaviour from the fabricated architectures upon Gd substitution and photon illumination. The findings are correlated with the increased charge carrier concentration and defect states existing within ZnGdO species, through appropriate mechanisms. (C) 2015 Elsevier Inc. All rights reserved.