The　application　of　homogeneous　electrocatalytic　reactions　in　energy　storage　and　conversion　has　driven　surging　interests　of　researchers　in　exploring　the　reaction　mechanisms　of　molecular　catalysts.　In　this　paper,　homogeneous　electrocatalytic　reaction　between　hydroxymethylferrocene　(HMF)　and　L-cysteine　is　intensively　investigated　by　cyclic　voltammetry　and　square　wave　voltammetry　for　which,　the　second-order　rate　constant　(k(ec))　of　the　chemical　reaction　between　HMF+　and　L-cysteine　is　determined　via　a　1D　homogeneous　electrocatalytic　reaction　model　based　on　finite　element　simulation.　The　corresponding　k(ec)　(1.1　(mol.m(-3))(-1).s(-1))　is　further　verified　by　linear　sweep　voltammograms　under　the　same　model.　Square　wave　voltammetry　parameters　including　potential　frequency　(f),　increment　(E-step)　and　amplitude　(E-SW)　have　been　comprehensively　investigated　in　terms　of　the　voltammetric　waveform　transition　of　homogeneous　electrocatalytic　reaction.　Specifically,　the　effect　of　potential　frequency　and　increment　is　in　accordance　with　the　potential　scan　rate　in　cyclic　voltammetry　and　the　increase　of　pulsed　potential　amplitude　results　in　a　conspicuous　split　oxidative　peaks　phenomenon.　Moreover,　the　proposed　methodology　of　k(ec)　prediction　is　examined　by　hydroxyethylferrocene　(HEF)　and　L-cysteine.　The　present　work　facilitates　the　understanding　of　homogeneous　electrocatalytic　reaction　for　energy　storage　purpose,　especially　in　terms　of　electrochemical　kinetics　extraction　and　flow　battery　design.　(C)　2021　The　Chemical　Industry　and　Engineering　Society　of　China,　and　Chemical　Industry　Press　Co.,　Ltd.　All　rights　reserved.