The synthesis of the LTA-type aluminophosphate could be achieved from aqueous reaction mixtures in the presence of a single organic template, i.e. the hexacosa-4,7,13,16,21,24-diaza-1,10-bicyclo[8,8,8]hexacosane ( Kryptofix222 ), this organic species being occluded in the large α cage of the structure. When F - ions were added in the synthesis medium, they acted as co-templates and were incorporated in the D4R units. Whether F - was present or not, the symmetry of the latter samples was cubic. In the presence of Kryptofix222 and tetramethylammonium cations, the obtained LTA-type AlPO 4 samples, with the (CH 3 ) 4 N + occluded in the β cages, are not fully crystallized and display also a cubic symmetry. In the presence of the three templates, the synthesis led to the formation of an AlPO 4 with a slightly distorted LTA-type structure. The symmetry of this compound is no longer cubic but rhombohedral. The value of the angle α = 88.2°, whereas the value of the parameter a is normal and close to 23.8 9. A description of this rhombohedral structure is proposed on the basis of a Rietveld refinement. The samples were characterized by several techniques, such as SEM, XRD, elemental analysis, thermal analysis and 1 3 C, 1 9 F, 3 1 P and 2 7 Al MAS NMR spectroscopy.