Surface characteristics of the {111} crystallographic planes of the III–V intermetallic compounds (zinc‐blende structure), and in particular those of , are discussed. The polarity of these compounds along the 〈111〉 directions leads to pronounced physical chemical differences between the {111} surfaces terminating with group III atoms and those terminating with group V atoms. Differences in etching, dislocation etch pit formation, and electrode potential are presented. Dislocation etch pits form on the group III surfaces and not on the group V surfaces of the six compounds investigated (, , , , , and ). A proposed interpretation is based on the relative reactivity of the group III and group V atoms as affected by their bond configuration and the polarity of the zinc‐blende structure.