Core-level binding energies of all atoms are reported for two series of compounds; MenMCl4−n and Me3MX (n = 0 → 4, M = Si or Ge, X = F, Cl, Br, I and (for M = Ge) CN, N3, and NCS ). Binding energy shifts are discussed using a 'whole-molecule' approach and are correlated with estimated atomic charges derived from an electronegativity-equalization procedure. Carbon 1s binding energies are also correlated to 13C n.m.r. chemical shifts.