We predict, on the basis ofabinitiototal energy calculations, that epitaxial growth of I‐VII compounds on III‐V substrates can be accomplished. We suggest specific combinations of I‐VII materials and III‐V substrates that minimize lattice mismatch and structural energy cost and show that the interface dipole can be minimal. This makes zinc‐blende I‐VII materials potential candidates for passivating layers, solid‐state laser applications, III‐V window material, and hole traps.