Biomass as a fuel is an important development for limiting greenhouse gas emissions and replacing fossil fuels. 1,3-Propylene glycol (1,3-PG) is a valuable chemical product obtained from bioglycerol hydrogenolysis. However, 1,3-PG is always mixed with ethylene glycol (EG) and 1,2-propylene glycol (1,2-PG), the properties of which are similar to those of 1,3-PG, making it costly to obtain a high-purity 1,3-PG product through distillation. Adsorption is a promising process for polyol separation, and a highly practical molecular sieve 10X (MS 10X) was employed as an adsorbent in this study to purify 1,3-PG from polyol mixtures. The adsorption capacity increased while the separation factor decreased with increasing pressure, and 160 kPa was chosen as a suitable operating pressure. The Freundlich isotherm described polyol adsorption on MS 10X well, and EG (1,2-PG) selectively adsorbed on MS 10X over 1,3-PG. This adsorption was a spontaneous physisorption process, and the entropy effect was the main driving force for selective adsorption. A pressure swing adsorption (PSA) system with dual beds for purifying 1,3-PG was designed rigorously by simulation, and the product purity exceeded 99.99%. Finally, a continuous distillation unit was designed to recover 1,3-PG, and the energy and equipment costs of both processes were compared. The designed PSA process could reduce energy costs by 60% and total annual cost by 39.6% over distillation.