The Madelung energies of A2+(B1/32+B2/35+) O32‐and A2+(B2/33+B1/36+) O32‐systems were calculated for different dopants on the A‐site. The theoretical results show that the higher‐valence dopant enhances the 1/2‐type (1:1) ordered arrangement of B‐site cations in A2+(B1/32+B2/32+)O32‐, whereas the lower‐valence dopant promotes the 1:1 ordering in A2+(B2/33+B1/36+)O32‐, and no doping promotes the 1/3‐type (1:2) ordering in the both systems. These calculation results are in agreement with the experimental observations of donor‐ and accep