Solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) was used for characterization of a series of metal containing microporous aluminophosphate of AFI type (MeAPO-5 with Me = Mg, Co, Zn and Mn). The position of Me atoms, whether in the framework or extraframework have been examined using 31P MAS NMR and bulk chemical analysis. It was found that 31P chemical shift values carried information about the distortion of MeAPO-5 structures by Me atoms which was correlated to the ionic size of Me atoms incorporated into their framework.