The (CNCH 2 CHCl) + ion has been observed in synchrotron radiation photoionization experiments for CH 3 CN + CH 2 CHCl van der Waals clusters, its appearance potential being 9.74 ± 0.02 eV. Experimental results indicate that it is a stable ion rather than a weakly bound cluster, which has been confirmed by ab initio HF3-21G * calculations. The structure of the ion has been determined by theoretical calculations.