The invention relates to a technique for coproduction of dimethyl carbonate and propylene glycol, in particular to a novel technique for purifying high-quality propylene glycol in the production process of dimethyl carbonate. The technical scheme includes the steps of reactive distillation, extractive distillation, separation of the dimethyl carbonate, the recovery and refining of carbinol, primary carbonization, first filtration of sodium carbonate crystals and refining of the propylene glycol. The invention solves the problem of low recovery rate of the propylene glycol, and the recovery rate of the propylene glycol can be above 95%. Meanwhile, the propylene glycol has more stable quality, with the purity reaching 99.99% and the chroma less than 10, thereby the propylene glycol totally meets the requirements for medical auxiliary material, daily cosmetics, top grade unsaturated resin and polyether. Meanwhile, the purity of the byproduct dipropylene glycol can be above 99.50%, thus improving the benefit of the equipment.