Potential characterization of deflected piezoelectric nanowires (NWs) is of great interest for current development of electromechanical nanogenerators that harvest ambient mechanical energy. In this paper, a Kelvin probe microscopy (KPM) technique hybridizing scanning KPM (SKPM) with atomic force microscope (AFM) surface-approach spectroscopy methods for characterizing in-plane piezoelectric potential of ZnO microwires (MWs) is presented. This technique decouples the scanning motion of the AFM tip from sample topography, and thus effectively eliminates artifacts induced by high topographical variations along the edges of MWs/NWs which make characterization by conventional SKPM inappropriate or impossible. By virtue of the topography/tip motion decoupling approach, the electrical potential can also be mapped in a three-dimensional (3D) spatial volume above the sample surface. Therefore, this technique is named 3DKPM. Through 3DKPM mapping, the piezopotential generated by a laterally deflected ZnO MW was determined by extracting the potential asymmetry from opposite sides of the MW. The measurement results agree well with theoretical predictions. Integrating an external bias to the MW sample allowed direct observation of piezopotential and carrier concentration coupling phenomenon in ZnO, opening a door toward quantitative microscopic investigation of the piezotronic effect. With further positioning refinements, 3DKPM could become a powerful technique for the characterization of piezoelectric potential and related effects in micro/nanostructures of high topographical variations, as well as development of MW/NW-based piezoelectric nanodevices.