Abstract <p>The ability to undergo reversible electron addition while preserving structural stability makes vanadium-containing polyoxometalates attractive objects for research in various fields of chemistry, in particular, the development of modern “green” processes. An efficient Pd-containing catalyst system based on Pd(OAc)₂ and a NaH₁₀P₄Mo₁₈V₇O₈₇ high-vanadium heteropoly acid for the two-stage oxidation of C₅–C₁₀ linear α-olefins to respective 2-ketones with a yield of over 93% in a two-phase water–organic medium has been developed. The system provides the achievement of economically promising process efficiency parameters; it is suitable for multicycle use and eliminates the need for high-pressure equipment in implementing the target reaction.</p>