AbstractVarious structures of CrAPO‐5 clusters are studied via density functional B3LYP exchange‐correlation method. The optimized structures are compared with data from X‐ray absorption. Their total energies and atomic net charges are also analyzed. Results indicate that the substitution of the aluminum site of an AFI framework by chromium is in general not feasible. The chromium ion is more likely docked in between two neighboring 12‐membered rings of the framework of AFI. To further verify our claim, the excitation energies of the representative chromium structures of CrAPO‐5 clusters are calculated via the TDDFT method. The results for excitation energies further support that Cr3+is not incorporated into the