Crystallization of Na2VOP2O7 from its aqueous solution results in formation, of a one-dimensional inorganic polymer {Na2VO-(H2O)P2O7 center dot 7H(2)O) (1). When this polymer is dehydrated at elevated temperatures this polymer undergoes a phase transition to form the two-dimensional framework beta-Na2VOP2O7, which although previously reported had been difficult to access. Exchanging lithium for sodium via ion-exchange chromatography results in formation of a discrete, cyclic, tetramer species, Li-g[VOP2O7(H2O)center dot 4H(2)O](4) (2). Isolation of crystalline beta-K2VOP2O7 using a dehydration procedure analogous to the one employed for the sodium derivative was unsuccessful. In contrast, we show that beta-K2VOP2O7 can be obtained from the amorphous phase K2VOP2O7 center dot nH(2)O (n = 0-7) upon thermal dehydration.