Anodic polarisation of a vanadium electrode has been studied in H3PO4 solutions and some phosphate solutions: LiH2PO4, NaH2PO4, KH2PO4 and NH4H2PO4. The anodic behaviour of a vanadium electrode showed similarities in weak concentrated H3PO4, in LiH2PO4 and NaH2PO4 solutions: the polarisation curve exhibited a current peak followed by current oscillations and then a current plateau. Concentrated H3PO4, 1M KH2PO4 and NH4H2PO4 solutions involved vanadium passivation with a very slight current density plateau. Yellow compound identified to VOPO4·2H2O was obtained after controlled potential oxidation of vanadium in 5–10M H3PO4. Green products were obtained in 1M phosphate solutions and in 1–3M H3PO4 on vanadium anode after controlled potential electrolysis. All these vanadophosphate compounds contained the monovalent cation which was present in the solution.