A process for the separation of ortho-, meta- and para-tolunitrile from ternary mixtures of isomers entails removing ortho-tolunitrile from these mixtures by distillation under pressures of from 10.sup.2 and 10.sup.5 Pa and with a reflux ratio of from 1:1 to 200:1, and distilling the remaining binary mixture of meta- and para-tolunitrile to concentrate to more than 75 mol-% para-tolunitrile, and freezing out the paratolunitrile at below 26.degree. C., and a process for the preparation of suitable ternary mixtures of isomers entails isomerization of pure ortho-, meta- or para-tolunitrile or mixtures thereof at from 380.degree. to 580.degree. C. on zeolite catalysts.