The synthesis, morphology, and magneto-transport properties of nanostructure-engineered charge-ordered Pr0.5Ca0.5MnO3 grown on ZnO nanowires are reported. The stability of the charge-ordering can be tuned, but more interestingly, the sign of the magnetoresistance is inverted at low temperatures. Coexistence of ferromagnetic clusters on the surface and antiferromagnetic phase in the core of the grains were considered in order to understand these features. This work suggests that such a process of growing on nanowires (NW) network can be readily extended to other transition metal oxides and open doors towards tailoring their functionalities.