In the present work we report the synthesis of four organic cation intercalated layered vanadium oxide bronzes by mild hydrothermal reactions: [(C6H5)(4)As](0.19)+V2O5, c similar to 17.7Angstrom; [(C6H5)(4)P](0.20)+V2O5, c similar to 17.2 Angstrom; [(C4H9)(4)P](0.19)+V2O5, c similar to 16.3Angstrom and [(C2H5)(4)N](0.58)(+) V2O5, c similar to 12.7 Angstrom. The layered solids were characterized using X-ray powder diffraction, electron microcopy, thermal analysis, FTIR and X-ray emission analysis. All the solids exhibited layered characteristics analogous to vanadium oxide xerogel. One-dimensional Patterson plots and electron density calculations suggest vanadium oxide bi-layer structure with organic molecules occupying inter-lamellar region. (C) 2004 Elsevier B.V. All rights reserved.