In doped ZnO nanocrystallites have established through a facile, low cost and high yield wet-chemical route. The X-ray diffraction measurements revealed the samples to be well crystallized, with a considerable shift in the prominent peak positions, indicating the successful substitution of In ions into the ZnO matrix. The particulate characteristic of the nanostructures was evaluated through the aid of electron microscopes, which revealed both the pristine and In doped ZnO nanocrystals to possess similar morphologies. The UV-vis absorption spectroscopic measurements revealed the doping of In3+ ions to lead with a red shift in the absorption edge of ZnO nanostructures. The Raman measurements provided conclusive evidence for the substitution of In ions at the Zn sites and their influence on the hexagonal lattice. The hybrid heterostructures made up of polypyrrole/ZnO and polypyrrole/Zn1-x InxO were established via drop casting a colloidal dispersion containing the prepared nanocrystallites and subsequently chemically in situ polymerizing the pyrrole monomers on the drop casted electrodes. The hybrid p-n junctions were then evaluated using the current-voltage characteristics. (C) 2014 Elsevier Inc. All rights reserved.