Neutron and X-ray diffraction experiments have shown that NaV2O5 consists of zig-zag V chains of average valence 4.5 rather than a charge ordered state at room temperature. Both these experiments revealed superlattice reflections below the phase transition temperature T-SP approximate to 34 K. The modulation below T-SP is due to displacements predominantly of V atoms for which we propose a model. (C) 1998 Elsevier Science Ltd. All rights reserved.