X-ray absorption and emission spectroscopies, supported by quantum mechanical calculations, were used to determine the architecture of Ti(IV) sites in Ti aluminophosphate AlPO4-5. The chemical sensitivity of the Kβ2,5 X-ray emission lines of Ti was exploited to monitor its local environment, proving that it mainly substitutes P in the framework, with a not negligible fraction substituting Al. Local structure of the substituted sites was found to be considerably deformed with respect to the AlPO4-5 original framework.