The adsorption characteristics of bismuth and antimony on III–V(110) substrates have been studied as a function of overlayer coverage and deposition conditions using low energy electron diffraction (LEED). We examine the different roles of chemical bonding and atomic size for determining surface ordering phenomena and epitaxy in these systems. LEED and Auger data were collected for monolayer range film thicknesses prepared on GaAs, InP, GaSb, InAs, and InSb substrates cleavedinsitu. BothIVand diffraction spot profiles were measured. Our results indicate that significant differences exist between the structure and surface chemical bonding of antimony and bismuth to III–V materials which were not revealed from previous studies using GaAs alone.