Herein, a general protocol for the preparation of a broad range of valuable N-heterocyclic products by hydrogenation of quinolines and related N-heteroarenes is described. Interestingly, the catalytic hydrogenation of the N-heteroarene ring is chemoselectively performed in the presence of other easily reducible functionalities including alkenes, ketones, cyanides, carboxylic acids, esters and amides. The key to successful catalysis relies on the use of a nanolayered cobalt-molybdenum sulfide catalyst prepared by a one-pot hydrothermal synthesis from cheap and abundant precursors. This non-noble metal-based heterogeneous system displays a tunable composition of phases that allows for catalyst regeneration. Its catalytic activity could be associated to the presence of a transient tertiary Co-Mo-S phase as well as to the composition of the mixed phase of cobalt sulfides.