Dinitrogen　activation　in　ammonia　(NH3)　synthesis　usually　obeys　either　the　dissociative　or　associative　route.　We　report　here　a　combination　of　dissociative　and　associative　routes　over　a　titanium　carbonitride　(TiCN)-promoted　Ru-based　catalyst　to　achieve　an　outstanding　NH3　synthesis　rate.　The　developed　Ru/3TiCN/ZrH2　catalyst　shows　a　superior　NH3　synthesis　rate　of　25.6　mmol　g(cat)(-1)　h(-1)　at　400　degrees　C　and　1　MPa.　Our　studies　reveal　that　TiCN　transfers　electrons　to　the　Ru　centers　and　reduces　the　aggregation　of　Ru　metal　particles　to　generate　more　B5　sites,　thus　accelerating　the　dissociation　of　N-2　to　form　NH3　via　a　dissociative　route.　Meanwhile,　the　facile　formation　of　nitrogen　vacancies　on　TiCN　assisted　by　Ru　enables　the　associative　mechanism　initiated　with　N-2　hydrogenation　to　form　*NNH.　The　synergistic　effect　of　Ru　and　TiCN　on　N-2　activation　via　integrating　the　dissociative　and　associative　mechanisms　accounts　for　the　superior　NH3　synthesis　rate　of　our　catalyst　under　mild　conditions.