A detail investigation on the stability and electronic properties for A 4 B 4 (A=Cu, Ag; B=As, Sn) metal–semiconductor alloy clusters, is performed in search for the stable and potential motifs. A very popular hybrid exchange–correlation functional, B3LYP as proposed by Becke is employed for this purpose, under the density functional formalism. To understand the possible potential of the predicted A 4 B 4 systems, frontier molecular orbitals (FMOs) are also analyzed along with the DFT based electronic parameters. The ground state structure for each of the A 4 B 4 systems is predicted. Also, a couple of nearly simple-cubic unit cells are identified for respective cluster-assembled/ bulk materials.