Indirect nuclear spin–spin (J) couplings between 31P, 27Al, and 17O are computed for Cl3POAlCl3, Ph3PO, Ph3PAlCl3, Al(H2O)63+, an aluminophosphate model system, and grossite model systems, using the B3LYP hybrid functional and the pcJ‐n and aug‐pcJ‐n basis sets. The results provide computational corroboration of the existence of J coupling constants between 31P, 17O, and 27Al of suitable magnitude for INEPT‐style experiments in which connectivity is established as a result of magnetization transfer using these couplings. Potentially useful correlations between structure (bond lengths, angles, dihedrals) and the coupling constants 1J(27Al,17O), 1J(31P, 17O), and 2J(31P, 27Al) are presented. Calculated values of near zero for both 1J(27Al,17O) and 2J(31P,27Al), depending on the molecule and the geometry, suggest that some structurally important correlations could be absent in NMR spectra which rely on magnetization transfers solely based on these isotropic coupling constants. Copyright © 2010 John Wiley & Sons, Ltd.