The AlPO4 content in CrPO4−AlPO4 (CrAlP-A) systems has a marked influence on thermal behavior, speeding up the transformation of amorphous CrPO4 to crystalline β-CrPO4. Thus, XRD analysis showed that amorphous systems are formed at AlPO4 loadings less than 50 wt.% and calcination temperatures below 1273 K. Moreover, on 50 wt.% AlPO4 developed crystalline β-CrPO4 in CrAlP-A systems for every calcination temperature. Besides, at 1273 K crystalline systems (β-CrPO4 and tridimite-AlPO4) are formed for every composition. Moreover, surface area at any calcination temperature increases with the rise in the AlPO4 content. Also, a surface area decrease on increasing calcination temperature is shown. Furthermore, CrAlP-A catalysts thermally treated below 1273 K only exhibited hydrogen bonded hydroxy groups (υO-H≃3450 cm-1).