A　comprehensive　understanding　of　both　redox　reactions　and　electrical　double　layer　capacitance　is　crucial　in　the　development　of　electrochemical　energy　conversion　and　storage　technologies.　Herein,　a　3D　hierarchically　porous　carbon　modified　electrode　is　investigated　by　both　experimental　and　theoretical　cyclic　voltammetry　based　on　finite　element　modeling.　An　electrochemical　reaction　rate　constant　of　1.06　x　10(-4)　m　s(-1)　is　initially　obtained　based　on　the　proposed　model　via　the　reversibility　analysis　on　cyclic　voltammograms.　Then　the　redox　reaction　of　ferrocyanide　on　an　FeN　hierarchically　porous　carbon　(FeN-HPC)　modified　electrode　is　carried　out　with　this　rate　constant.　A　comparison　of　voltammetric　waveforms　indicates　that　the　redox　behavior　of　ferrocyanide　is　independent　of　the　electrical　double　layer　capacitance　which　stemmed　from　the　porous　structure　and　morphology　of　FeN-HPC.　Correspondingly,　a　specific　capacitance　of　68.80　F　g(-1)　is　obtained　with　a　mass　loading　of　4　mu　g　on　the　substrate.　Moreover,　a　comparison　of　simulated　ferrocyanide　and　ferricyanide　concentrations　against　both　applied　potential　and　the　distance　to　the　electrode　surface　further　verifies　the　independence　of　the　redox　reaction　from　the　electrochemical　capacitance.　In　summary,　this　study　facilitates　the　understanding　of　the　redox　reaction　on　a　3D　hierarchically　porous　carbon　modified　electrode,　which　is　important　in　the　development　of　energy-related　electrode　fabrication.