The azo- and hydrazo compounds are of great importance in pharmaceuticals, agrochemicals, and chemistry. The controlled reduction of nitroarenes to their coupled products such as aromatic azo and hydrazo compounds has been an interesting area of research synthetically and mechanistically. Herein, we report that the chemoselective catalytic hydrogenation of nitrobenzenes to hydrazobenzenes via azobenzenes can be achieved over gold nanoparticles supported by hexagonal boron nitride nanoplates. It is found that the catalytic process can be successfully conducted not only in N-2 but also in air with isopropanol alcohol/KOH. Complete conversion of nitrobenzenes and high selectivity of azobenzenes and hydrazobenzenes have been achieved in one pot under N-2 or air atmosphere. Furthermore, as usual unstable intermediates in the reduction process of nitrobenzenes, azobenzenes and hydrazobenzenes can be alternatively harvested as the main product by controlling reaction time or atmosphere. This work shows promise for direct and chemoselective synthesis of azo- and hydrazo compounds under mild conditions in a controllable manner. (C) 2018 Elsevier Inc. All rights reserved.