NovelV(III) compound, V(OH)(HCOO)₂ has been synthesized by controlled current electrolysis route. V(OH)(HCOO)₂ precipitation during electrolysis was found to depend on both pH and concentration of V(III) in solution. It is an ionic V(III) compound with mild associated organic anion. The compound readily dissolves in pure water but subsequently precipitates out as polymer depending upon concentration and aging duration. However a stable aqueous solution with significantly high V(III) concentration could be prepared from it by adding a suitable complexing agent like nitrilotriacetic acid (NTA) and citric acid. These complex formulations will have potential application for nuclear power plant application and vanadium redox batteries. Electrochemical evaluation of the reduction characteristics of the compound on glassy carbon and stainless steel electrodes has established the varying effect of free acid at these surfaces. Part consumption of current for proton reduction on stainless steel electrodes and blocking of active sites by H⁺ adsorption on carbon surfaces was observed. Thus, a high surface area carbon based electrodes will be better suited for high current efficiency during vanadous solution preparation by electroreduction while stainless steel electrodes may be used for efficient hydrogen generation from organic acids.