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　N2　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　N2　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.　©　2018　Elsevier　Inc.