We describe the first detailed X-ray photoelectron spectroscopic (ESCA) examination of the surface and near-surface chemistry of VPI-5, AlPO4-8, and AlPO4-11 as well as pseudo-boehmite and several AlPO4’s of "compromized integrity". A distinct set of core level binding energies was determined and compared to related spectra for cloverite (a gallium phosphate-based sieve) and several zeolites. ESCA line shifts are interpreted in terms of the relative degree of ionicity (covalency) of the Al-0 and P-O bonds in the framework.