The activity of the sodium salts of vanadium-doped phosphomolybdic acid was assessed in the oxidative esterification reaction of benzaldehyde with hydrogen peroxide in alkyl alcohol solutions. The effect of main reaction parameters, such as temperature, catalyst load, vanadium doping level, and reactant stoichiometry, on the conversion and reaction selectivity was investigated. Among the tested heteropoly salts, Na4PMo11VO40 was the most active and selective catalyst, achieving almost complete conversion of benzaldehyde and high ester selectivity regardless of the alcohol investigated. The efficiency of the catalyst was correlated with its vanadium content. The size of the carbon chain of alcohol and the steric hindrance on the hydroxyl group played a key role in the reaction selectivity. While methyl and ethyl alcohols selectively provided the ester as the main product (ca. 90–95%) and benzoic acid as a subproduct, the other alcohols also afforded acetal, a condensation product, and benzaldehyde peroxide, an oxidation reaction intermediate, as secondary products. The use of an inexpensive, environmentally benign, and atom-efficient oxidant, mild conditions, and short reaction times were the positive aspects of this one-pot process.