A process for preparing caprolactam by cyclization of 6-aminocapronitrile in the presence of water at elevated temperature and in the presence or absence of a catalyst and a solvent, comprises a) removing from the cyclization reaction effluent ("reaction effluent I") caprolactam and all components boiling higher than caprolactam ("high boilers"), b) treating the high boilers of stage a) with phosphoric acid and/or polyphosphoric acid at from 200 to 350.degree. C. to obtain a reaction effluent II, and c) removing caprolactam formed and any 6-aminocapronitrile from reaction effluent II of stage b) to obtain separation from unconverted high boilers and acid used.