We report on a method based on cross-sectional scanning photoelectron microscopy and spectroscopy (XSPEM/S) for studying electronic structure of III-nitride surfaces and interfaces on a submicrometer scale. Cross-sectional III-nitride surfaces prepared by in situ cleavage were investigated to eliminate the polarization effects associated with the interface charges/dipoles normal to the cleaved surface. In contrast to the as-grown polar surfaces which show strong surface band bending, the cleaved nonpolar surfaces have been found to be under the flat-band conditions. Therefore, both doping and compositional junctions can be directly visualized at the cleaved nonpolar surfaces. Additionally, we show that the "intrinsic" valence band offsets at the cleaved III-nitride heterojunctions can be unambiguously determined.