The invention discloses a recovery process of caprolactam refining raffinate. The caprolactam refining raffinate and oxidant are mixed according to the weight part ratio of 3.1:1-3.3:1, reacting while stirring at 32-40DEG C under normal pressure; after the reaction is carried out for 30-40 minutes, the reaction continues for 80-90 minutes while stirring at 78-82DEG C under normal pressure; the products are extracted at ambient temperature and pressure by using an extractant, and an organic extract phase which contains the caprolactam is returned to a water back-extraction system of a CPL device. The recovery process can eliminate reducing impurities and impurities with the properties which are similar to those of the caprolactam in the caprolactam refining raffinate, in particular to impurities which influence 290nm extinction value, PM value and V.B, thus recovering and preparing high-purity caprolactam. By adopting the recovery process, a company which has an annual output of 100 thousand tons of caprolactam can recover 1600-2000 tons of the caprolactam per year which is equivalent to 30 million yuan, thus improving the annual output and the economic benefit and reducing the unit consumption of the caprolactam.