In this communication, we report the results of the structural and transport studies performed on ZnO/La_0.7Ca_0.3MnO₃/LaAlO₃ (ZnO//LAO) heterostructure grown using simple, low cost, vacuum free and environment friendly chemical solution deposition (CSD) method. ZnO is found to be polycrystalline while LCMO film orientations suggest its single crystalline growth, parallel with the crystallographic orientations of LAO substrate. Double peak transition behavior, observed in the R – T, has been discussed on the basis of phase coexistence scenario. Charge transport behavior and charge conduction mechanisms have been investigated by performing current–voltage (I–V) characteristics at different temperatures. Various electronic and thermal processes have been proposed as sources of backward diode like characteristics observed across ZnO/LCMO interface. Complex variations in electroresistance (ER) have been discussed on the basis of charge injection, depletion region modifications, tunneling, breakdown and thermal processes.