Developing　efficient　and　robust　catalysts　for　hydrogen　production　by　ammonia　decomposition　is　of　importance　towards　the　＇zero-carbon＇　economy.　Herein,　a　series　of　B-site　Ni-　and　Co-doped　A-site-deficient　SrTiO3　perovskite　(Sr0.9Ti0.8Ni0.1Co0.1O3-δ,　STNC)　with　the　in　situ　exsolution　of　NiCo　nano-alloys　were　fabricated　under　reducing　atmosphere.　The　Ni–Co/STO　(SrTiO3)　catalyst　derived　from　STNC　shows　much　higher　activity　for　ammonia　decomposition　than　those　Ni　and　Ni–Co　based　catalysts　fabricated　by　impregnation.　The　STNC　derived　sample　can　produce　32.6　mmol　gcat−1·min−1　hydrogen　at　600　°C,　2.2　and　1.9　fold　higher　than　those　of　Ni/STO　and　Ni–Co/STO.　Furthermore,　the　synthesis　methods　including　the　Pechini,　hydrothermal　and　ball　milling　methods　were　investigated　for　the　preparation　of　the　exsoluted　Ni–Co　catalysts　toward　ammonia　decomposition.　The　STNC–HT　catalyst　by　hydrothermaldemonstrated　an　excellent　performance　and　reached　70%　and　a　near　equilibrium　conversion　of　ammonia　under　600　and　650　°C　with　a　WHSV　of　30,000　mL　gcat−1h−1.　The　relationship　between　structure　and　performance　was　further　studied　by　a　series　of　characterizations.　In　addition,　the　STNC–HT　catalyst　was　employed　in　the　direct　ammonia　solid　oxide　fuel　cells,　in　which　the　performance　is　closely　related　to　the　ammonia　decomposition　activity,　and　shows　a　satisfying　power　density　of　99.3　mW　cm−2.　Generally,　we　identified　an　approach　to　engineer　catalysts　with　enhanced　activity　for　the　ammonia　utilization　as　energy　vectors　in　our　work.　©　2024　Hydrogen　Energy　Publications　LLC