We report on the Li electrochemical reactivity of amorphous and crystalline VP2, synthesized by ball-milling and by 600 degrees C heat treatment of a ball-milled sample, respectively. The amorphous sample can reversibly react with 3.5 Li per formula unit as compared to solely 2.5 for the crystalline one. However in both cases there is a rapid capacity decay upon cycling that is more pronounced in the case of the crystalline sample. Complementary X-rays, HTREM and NMR tend to show that the Li reactivity mechanism differs from the classical conversion reactions since neither V nanoparticles northe formation of Li3P were detected, as opposed to some of the other MP2 compounds (M=NiorCu). Besides structural phase variations within the 3d metal-based binary phosphide series, the possibility of a change in the nature of the redox centre upon lithiation from cation (M) to anion (P) is evoked. (c) 2007 Elsevier B.V. All rights reserved.