AbstractCrosslinking experiments for immobilization of the well‐known chiral stationary phases XE 60‐L‐valine‐(S)‐ and XE 60‐L‐valine‐(R)‐α‐phenylethylamide within capillary columns have been successfully carried out. Crosslinking was also obtained with mixtures of the chiral compound acrylyl‐L‐valine‐(S)‐α‐phenylethylamide and the polyethylene glycol Carbowax 20M. Immobilization of 75% to 90% was achieved by crosslinking the polymeric chiral phases, but sometimes up to 100% of these phases remained within the columns after the usual subsequent solvent treatment. The crosslinking of Carbowax 20M with acrylyl‐L‐valine‐(S)‐α‐phenylethylamide led to a chiral polymer of a polarity different from that