A combination of the photoelectron spectrometrics and density functional theory calculations has confirmed bond-order-length-strength (BOLS) predictions on the atomic undercoordination induced local bond contraction, charge densification and bond energy entrapment of lithium (Li) atomic clusters and layer-resolved Li(1 1 0) skins. Analysis also derives the energy level of an isolated Li atom and its shift upon bulk and skin formation, which is beyond the scope of currently available approaches.