A solid-state NMR method combining Al-27 multiple-quantum magic-angle spinning (MQMAS) and P-31{Al-27} heteronuclear correlation (HETCOR) has been applied for the structural analysis of amorphous AlPO4. We obtained a correlation between the isotropic chemical shifts of P-31 in PO4 and of Al-27 in each AlOn (n = 4, 5, and 6) distributed by the amorphous structure.