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Abstract Electrocatalytic proton reduction to form dihydrogen (H₂) is an effective way to store energy in the form of chemical bonds. In this study, we validate the applicability of a main‐group‐element‐based tin porphyrin complex as an effective molecular electrocatalyst for proton reduction. A PEGylated Sn porphyrin complex (SnPEGP) displayed high activity (−4.6 mA cm⁻²at −1.7 V vs. Fc/Fc⁺) and high selectivity (H₂Faradaic efficiency of 94 % at −1.7 V vs. Fc/Fc⁺) in acetonitrile (MeCN) with trifluoroacetic acid (TFA) as the proton source. The maximum turnover frequency (TOF_max) for H₂production was obtained as 1099 s⁻¹. Spectroelectrochemical analysis, in conjunction with quantum chemical calculations, suggest that proton reduction occurs via an electron‐chemical‐electron‐chemical (ECEC) pathway. This study reveals that the tin porphyrin catalyst serves as a novel platform for investigating molecular electrocatalytic reactions and provides new mechanistic insights into proton reduction.