A series of chiral enantiomerically pure aziridines containing a phosphine moiety were synthesized and successfully applied as organocatalysts in asymmetric intramolecular Rauhut–Currier reactions of p-quinone derivatives. The desired chiral phenols were achieved in high chemical yields and with satisfactory values of enantiomeric excess (up to 98% ee, in some cases). The stereochemical course of the title reaction may be controlled by the use of an appropriate enantiomer of the catalyst. The individual enantiomers of the organocatalyst led to the formation of specific enantiomers of the chiral product.