The Mn+1AXn layered carbide/nitride-derived phases, where M is an early transition metal, A is an A-group element and X is N or C, have an unusual combination of mechanical, electrical and thermal properties. The surface and crystal-chemistries of several recently synthesized n=1 members have been investigated by X-ray photoelectron spectroscopy. The results show that the constituent species are characterized by low binding energies, sometimes exceptionally so. The C 1s energies are in the lower end of the range for carbides, at 281.1-282.0 eV. The M-species-Ti, V, Nb and Hf-have binding energies at or below those corresponding to the elemental metallic state. The binding energies of the A-species in apparent planar coordination-In, Ge, As and Al-are quite exceptional, being 0.5-2 eV below those corresponding to the elemental state. Those results suggest that screening of the A-group species is derived from out-of-plane interactions, while the XPS signatures of the species associated with the MX blocks are reminiscent of those obtained from the relevant carbide phases.