There is now growing interest in the potential of thiocyanate analogues of PBAs as functional materials, and we have re- ], in part inspired by previous partial reports of other transition metal thiocyanates hexthiocyanatobismuthates . This aliovalent substitution introduces a high concentration of defects which, when combined with the low symmetry of the parent structure, produces longrange defect order. The presence of long-range order allows us to carry out detailed crystallographic investigations of both the identities and distribution of defects. We find that despite the close similarities between the chemistry of these transition metals, the defect structures are diverse, in both local structure and long-range order. We show that the point defects in these frameworks include [Bi(SCN) 6 ] 3 -vacancies, water clusters of up to 20 molecules, anti-site defects, and incorporation of interstitial charge-balancing cations. These point defects order into complex superlattice patterns which are, to the best of our knowledge, unknown in perovskites, both hybrid and conventional. We also find that where lower coordination-numbers are feasible for the transition metal, e.g. Zn 2+ , new ordered structures can be favoured over defective frameworks. The range of chemistry found in these materials suggests that control over defects could produce surprising new chemical functionality throughout molecular perovskites. vacancies are occupied by molecular aqua-Mn(II) thiocyanate complexes with average composition Mn(H 2 O) 5 (NCS) + , connected to the framework by hydrogen bonds [Fig. ]. The positive charge on the molecular complex is balanced by an additional terminal framework thiocyanate which replaces a bound water.