The　protonic　ceramic　fuel　cells　(PCFCs)　can　convert　the　chemical　energy　of　fuel　directly　into　electric　power,　with　the　advantages　of　high　efficiency　and　alternative　fuel　range　at　intermediate　temperatures.　Ammonia　has　been　regarded　as　a　promising　fuel　for　PCFCs　due　to　its　carbon-free　and　hydrogen-rich　properties,　high　volumetric　energy　density　and　easy　storage/transportation.　However,　the　performance　of　ammonia　PCFCs　(NH3-PCFCs)　is　far　inferior　to　the　hydrogen　PCFCs　(H2-PCFCs)　because　of　the　sluggish　and　complex　kinetics　at　anodes.　In　this　study,　we　established　an　elementary　reaction　kinetic　model　for　NH3-PCFCs,　investigated　the　effect　of　reaction　parameters,　anode　components　and　reaction　partition,　and　explored　the　coupling　mechanism　between　the　ammonia　decomposition　and　electrochemical　reaction.　Importantly,　the　ammonia　decomposition　and　electrochemical　reaction　can　be　flexibly　regulated　by　adjusting　anode　parameters,　then　affecting　the　performance　ratio　of　NH3-PCFCs　and　H2-PCFCs.　The　detailed　rate-determining　steps　were　further　identified　by　experimental　and　model　analysis.　Thus,　the　ammonia/hydrogen　performance　ratio　of　the　cell　can　exceed　95%　at　550°C　after　accelerating　the　ammonia　decomposition　reaction.　Our　work　provides　insights　into　the　kinetics　in　NH3-PCFCs　for　improving　their　performance　with　optimization.　©　2024　American　Institute　of　Chemical　Engineers.