a b s t r a c t A TOF-SIMS VG Ionex IX23LS with upgraded data acquisition and control system was used to study the secondary emission of negative atomic and cluster ions of non-metallic elements (P, As and Sb) upon a 19 keV Ga + bombardment of non-degenerated III–V semiconductors (GaP, GaAs, GaSb, InP, InAs and InSb) with prior neutral Cs deposition from a getter dispenser. It was found that surface cesiation enhances the peak intensity of all negative ion species; in the case of atomic ions, the greatest increase (360) was observed for P − emitted from InP. Such an enhancement was larger for In-based than for Ga-based compounds. We explained that in terms of an electronegativity difference between the composing atoms of III–V semiconductors. The greater electronegativity difference (bond ionicity) of In-based compounds resulted in the greater Cs-induced work function decrease leading to a higher increase in the ionization probability of secondary ions.