As-synthesized AlPO4-5 aluminophosphate molecular sieve prepared in a fluoride medium, using the quaternary tetrapropylammonium (TPA(+)) cation template, is characterized by a variety of solid-state NMR techniques. F-19 MAS spectra show two distinct populations, with the same isotropic chemical shift. While P-31 MAS experiments distinguish four different crystalline environments, both F-19-P-31 CP-MAS and HETCOR experiments reveal that only two signals belong to the AlPO4-5 framework, whereas the remaining two are attributed to crystalline byproducts. Al-27 MAS and 3Q-MAS spectra indicate, in addition to the tetrahedral environment, the presence of pentacoordinated Al species in close proximity to fluorine atoms, as is additionally shown by the F-19-Al-27 HETCOR experiment. An Al-27-{F-19} REDOR experiment strongly supports the existence of an Al-F bond (r(Al-F) < 2 Angstrom which forms the fifth coordination position of one of the twelve aluminum sites of the unit cell.