The invention belongs to the technical field of thionyl chloride production and mainly relates to a withdrawal method and device for improving product quality in the refining process of thionyl chloride. The method comprises a side withdrawing and product column top vacuum operation system and comprises the specific steps of (a), after crude thionyl chloride from the bottom of a light component removal column enters a product column for distillation and separation, withdrawing finished thionyl chloride from the side; (b), after crude thionyl chloride with little sulfuryl chloride withdrawn from the top is cooled via a top condenser, entering the crude thionyl chloride into a reflux tank, and reflowing to the top of the product column via a reflux pump; (c), extracting via a vacuum ejector pump through a top condenser gaseous pipe, absorbing by circulating liquid, and delivering to the system for re-distillation. The method provides greatly improved product quality, thionyl chloride purity is 99.95% and above, product column energy consumption is decreased by 5%, energy saving effect is significant, economic benefit is greatly improved, and operation is convenient.