The traditional manufacturing process of 1,3-dioxolane requires high investment and energy consumption. A reactive distillation with pressure-swing distillation process is proposed as an attractive candidate based on the process simulation results in this work. To simulate the reactive distillation process, the kinetics experiments of formaldehyde aldolization with ethylene glycol were performed over NKC-9 cationic-exchange resin catalyst at 353-368 K. Byproducts were observed, and the batch distillation experiment were carried out to determine the boiling point temperatures ranking. A calculation strategy of aqueous and ethanediolic formaldehyde solutions was developed to solve the vapor-liquid equilibrium. The sensitivity analysis result shows that the yield of 1,3-dioxolane could be improved to 0.995 in the reactive distillation column, and high-purity 1,3-dioxolane (99.9 wt %) can be obtained in the following pressure-swing distillation process. The research achievements provides a new 1,3-dioxolane production process, which has an advantage in equipment integration.