Electrocatalytic oxidation has been proven as a sustainable and promising alternative to traditional chemical transformation, but its further development is limited by the use of noble-metal electrocatalysts. Herein, a polyoxometalate-based electrode material, H₅PMo₁₀V₂O₄₀@CTF (denoted as PMo₁₀V₂@CTF), has been successfully fabricated through electrostatic assembly of a molecular polyoxometalate catalyst, PMo₁₀V₂, with a porous cationic covalent triazine framework (CTF), which, to our knowledge, represents the first combination of polyoxometalate with a cationic CTF. The resulting PMo₁₀V₂@CTF exhibits high activity for the selective electrocatalytic oxidation of alcohols to aldehydes, achieving 99% conversion of benzyl alcohol, over 99% selectivity of benzyl aldehyde, and at the same time near unity H₂ production. Notably, the reported electrocatalytic system presents good atom economy, high energy conversion (96% faradaic efficiency), remarkable catalytic activity and robustness for at least eight recycles. Based on the various experimental and spectroscopic analyses, a possible catalytic mechanism was proposed, revealing that such excellent electrocatalytic performance is attributed to the versatile redox ability of PMo₁₀V₂ and the good porosity and adsorption property of the CTF in the constructed PMo₁₀V₂@CTF composite.