In order to recover caprolactam from wastewater in the production of caprolactam from toluene, the behavior of caprolactam extraction with chloroform as extractant was studied. The influences of the pH of the solvent, extraction temperature and contact time on the extraction process were investigated. The experimental results showed that the extraction process is a fast extraction process. The distribution ratio increases with the increase of pH of the aqueous solution and reaches its maximum when pH=7. It was found that ammonium sulfate and 1-sulfonic acid-1-cyclohexanecarboxylic acid in the aqueous solution have the salting-out effect which can enhance the distribution ratio. The extraction temperature has only a little effect on the extraction process. The distribution equilibrium relation of caprolactam with chloroform in aqueous and organic solution with pH=7 was determined and the extraction enthalpy of 2.86 kJ?mol-1 was obtained by experimental measurement. When the volume ratio of organic to aqueous phase is 1, the recovery yield of 3-stage cross-flow extraction is above 98%. The results of cross-flow extraction for industrial wastewater with Chloroform showed that Chloroform is the suitable solvent for the recovery of caprolactam from industrial effluent.