Single-site CeAlPO-5 with Al/Ce ratios 25, 50, 75, 100 and 125 were synthesized hydrothermally in fluoride medium. The XRD patterns of CeAlPO-5 exhibited characteristic reflections of AlPO-5. 27Al MAS-NMR of CeAIPO-5(25) showed two unusual peaks at -20.78 and -71.35 ppm due to delocalization of cerium unpaired electron. However, 31P MAS-NMR exhibited the usual characteristic peak similar to that of AlPO-5. Vapour phase oxidation of toluene in air over CeAlPO-5 yielded benzaldehyde with high toluene conversion. The time on stream study established the stability of the catalyst. This catalyst can also be used for the selective oxidation of other alkyl aromatics.