In this article, we present a detailed study of the reach distance‐layer structure of the De Bruijn and Kautz digraphs, and we apply our analysis to the performance evaluation of deflection routing in De Bruijn and Kautz networks. Concerning the distance‐layer structure, we provide explicit polynomial expressions, in terms of the degree of the digraph, for the cardinalities of some relevant sets of this structure. Regarding the application to defection routing, and as a consequence of our polynomial description of the distance‐layer structure, we formulate explicit expressions, in terms of the degree of the digraph, for some probabilities of interest in the analysis of this type of routing. De Bruijn and Kautz digraphs are fundamental examples of digraphs on alphabet and iterated line digraphs. If the topology of the network under consideration corresponds to a digraph of this type, we can perform, in principle, a similar vertex layer description.