Interface structure and epitaxial growth of NiAl on III-V or 11-VI zinc-blende substrate have been studied by using the embedded atom method. Simulation showed that the {001} NiAl on {001} zinc-blende substrate forms a stable epitaxy only if a Ni monolayer is predeposited. A new model for the NiAl-zinc-blende substrate interface is proposed. The investigation of d-spacing changes in the intermetallic overlayer showed anomalies near the interface and free surface, and this behaviour is expected to affect the properties of the epilayer.