A detailed electrochemical study of Li insertion in the α-form of VOPO 4 and the optimization of the cycling performance are presented. The redox process occurs in one step close to 3.76 V, along with a phase transition. In order to improve the intercalation kinetics, the electronic conductivity was optimized by introducing a mixed valency, and the ionic conductivity was favored by introducing 'pillaring' molecules or ions in the interlayer space. In this way, the electrochemical behaviors of α-VOPO 4 .2H 2 O, α-Na x VOPO 4 , α-K x VOPO 4 and α-Mg x VOPO 4 (0=<x=<1) have been studied: the hydrate compound shows a good specific capacity (100 mA h/g at a C/5 regime), but a poor cyclability was mainly because of water oxidation. The inserted large alkaline ions improved the cyclability up to 80 cycles (Na + ) or over 100 cycles (K + ). Enhancements of the VOPO 4 specific capacity have been obtained as well by mechanical ball-millings.