The synthesis of compounds of the type CsAIIIMIVO4 and (Cs,Rb)AIIPO4 (AIII = Al, Ga, Fe; AII = Ni, Co, Cu; M = Si, Ge, Ti,), using gel decomposition techniques at high temperatures is described. Several new materials in this family have been characterised using powder X-ray diffraction and are shown to adopt the zeolite ABW framework topology. Evidence for the large monovalent cation templating the formation of the ABW framework is presented. Extension of the method to other AIII and MIV (A = Mn, Co, B, In; M = Sn, Zr) framework cations, which are known to adopt tetrahedral geometry in other structures, has proved unsuccessful.