Several　copper　corrole　complexes　were　synthesized,　and　their　catalytic　activities　for　hydrogen　(H-2)　evolution　were　examined.　Our　results　showed　that　substituents　at　the　meso　positions　of　corrole　macrocycles　played　significant　roles　in　regulating　the　redox　and　thus　the　catalytic　properties　of　copper　corrole　complexes:　strong　electron-withdrawing　substituents　can　improve　the　catalysis　for　hydrogen　evolution,　while　electron-donating　substituents　are　not　favored　in　this　system.　The　copper　complex　of　5,15-pentafluorophenyl-10-(4-nitrophenyl)corrole　(1)　was　shown　to　have　the　best　electrocatalytic　performance　among　copper　corroles　examined.　Complex　1　can　electrocatalyze　H-2　evolution　using　trifluoroacetic　acid　(TFA)　as　the　proton　source　in　acetonitrile.　In　cyclic　voltammetry,　the　value　of　i(cat)/i(p)　=　303　(i(cat)　is　the　catalytic　current,　i(p)　is　the　one-electron　peak　current　of　1　in　the　absence　of　acid)　at　a　scan　rate　of　100　mV　s(-1)　20　degrees　C　is　remarkable.　Electrochemical　and　spectroscopic　measurements　revealed　that　1　has　the　desired　stability　in　concentrated　TFA　acid　solution　and　is　unchanged　by　functioning　as　an　electrocatalyst.　Stopped-flow,　spectroelectrochemistry,　and　theoretical　studies　provided　valuable　insights　into　the　mechanism　of　hydrogen　evolution　mediated　by　1.　Doubly　reduced　1　is　the　catalytic　active　species　that　reacts　with　a　proton　to　give　the　hydride　intermediate　for　subsequent　generation　of　H2.