Usefulness of W substitution for improvement of battery performance of LiMn2O4 cathode was investigated. Small amounts of tungsten were incorporated into LiMn2O4 spinel instead of available Mn. For this purpose, two sources of tungsten (metallic W or WO3) were examined. W concentration and source have significant influence on both morphology and electrochemical behavior of W-substituted LiMn2O4 spinels. W substitution of LiMn2O4 spinel can lead to the formation of uniform spinel particles and improved battery performance. Cyclic voltammetric behaviors of the samples were examined in an aqueous solution, and Li diffusion process was investigated for different cases. The best case was the LiW0.01Mn1.99O4 spinel prepared from metallic W powder, as exhibits excellent rate capability, but better cycleability was observed for the LiW0.01Mn1.99O4 spinel prepared from WO3. This means that because of significant influence of the dopant source, this parameter should be chosen in respect with the desire improvement.