The intercalation behavior of layered a-phase vanadyl phosphate, alpha-VOPO4 center dot 2H(2)O (alpha-VP), with alkylamine was investigated by V-51 solid-state NMR in combination with powder XRD. The XRD results show that the amines form bimolecular layers upon intercalation. For the intercalation with short chain amines (propylamine, pentylamine, and hexylamine), the C-C chain of the amines is tilted with respect to the inorganic basal plane. The amines with a longer alkyl chain (dodecylamine and hexadecylamine) tend to adopt an orientation where the C-C chain direction is perpendicular to the VP layer. For the amine with eight carbon atoms (octylamine), the intercalation results in two coexisting phases with different chain orientations. V-51 solid-state NMR was used to directly probe the effect of intercalation on the metal center environments. Both V-51 magic-angle spinning and static spectra of alpha-VP intercalated with different amines were obtained at different magnetic fields, and they are sensitive to intercalation. The intercalation induces the V-51 isotropic chemical shift to move toward deshielded direction. V-51 chemical shielding parameters such as the span are sensitive to the orientation of the amine chain with respect to the VP basal plane. For the V centers interacting with the amines having a tilted orientation, the V-51 span gradually decreases with increasing alkyl chain length. However, the span of the V-51 atoms interacting with the amines perpendicular to the VP layer is larger and independent of the length of the alkyl chain. The V-51 NMR data indicate that for the alpha-VPs intercalated with long-chain amines, such as dodecylamine and hexadecylamine, the amines can assume both tilted and perpendicular orientations.