Measurements of the voltage and temperature dependence of tunneling in Ge and GaSb are presented which confirm the close proximity of the (000) and (111) conduction band edges in these materials. In the case of Ge, the energy separation of these edges is found to increase with increasing donor concentration.Tunneling in the indirect semiconductor GaP shows no evidence for indirect (phonon‐assisted) tunneling transitions. It is believed that tunneling in the junctions which we studied proceeds via deep‐level impurities rather than between conduction and valence bands directly, thereby eliminating the requirement of wave number conservation.Revised values for the zone‐center longitudinal optical phonon energies as deduced from tunneling data in 3–5 and lead salt semiconductors are presented.