A series of M2+O-Cr2O3-P2O(5) (M+ = Na, K) materials have been synthesized via hydrotherinal route. The resultant materials were characterized by SEM, powder XRD, FTIR and magnetic Susceptibility Studies. The powder X-ray studies revealed that the Na2O-Cr2O3-P2O5 materia has crystallized in orthorhombic system with cell parameters a = 20.76764, b = 8.86712, c = 8.53437 angstrom, v = 1571 and K2O-Cr2O3-P2O5 material has crystallized in monoclinic system with and cell parameters a = 11.8 194, b = 6.1518, c = 11.0347, beta = 94.846, v = 799.47 angstrom. Repetitive hydrothermal treatment yielded improved crystalline materials. Magnetically these are paramagnetic, however, the mu(eff) decreased as the size of the material increased. (c) 2005 Elsevier B.V. All rights reserved.