The construction of metal-anion arrays within Dion-Jacobson-type (DJ) perovskites was studied. A variety of hosts readily react with CuCl2 to produce compounds of the form (CuCl)[A'n-1(M,M')nO3n+1] (A' = alkaline earth, rare earth or Bi; M/M' = Nb, Ta, and/orTi; n = 2, 3). In contrast, CuBr2 only reacts with some of these hosts; this difference relative to the chloride may simply be a size effect. The formation of metal-anion arrays with other transition metals has also been examined. (FeCl)LaNb2O7 can be readily prepared from FeCl2, while reactions with FeBr2and NiCl2 under similar reaction conditions result in compounds of the formM0.5LaNb2O7 (M = Fe, Ni). The reductive intercalation of lithium and sodium into (CuCl)LaNb2O7 was also examined and was found to produce new compounds that have a large layer expansion.