The valence‐band discontinuities at various wurtzite GaN, AlN, and InN heterojunctions were measured by means of x‐ray photoemission spectroscopy. A significant forward–backward asymmetry was observed in the InN/GaN–GaN/InN and InN/AlN–AlN/InN heterojunctions. The asymmetry was understood as a piezoelectric strain effect. We report the valence band discontinuities for InN/GaN=1.05±0.25 eV, GaN/AlN=0.70±0.24 eV, and InN/AlN=1.81±0.20 eV, all in the standard type I lineup. These values obey transitivity to within the experimental accuracy. Tables of photoemission core level binding energies are reported for wurtzite GaN, AlN, and InN.