Electrochemical reduction of the hexavalent chromium compounds, a serious environmental pollutant and carcinogen, to a nontoxic Cr(III) species is of significant research interest in interdisciplinary areas. Due to its high oxidation potential (1.36 V vs RHE) and associated surface fouling problems with organic-electrocatalyst systems, expensive precious metalbased electrodes like Au, Ag, Pt, and Pd have been widely used for this purpose. Herein we report, an in situ electrochemically prepared highly redox-active Binol species (Binol-Redox)-impregnated carbon nanofiber-modified electrode (CNF@Binol-Redox), E o ′ = 0.50 V versus Ag/AgCl and surface excess value (Γ Binol-Redox ) = 32.5 × 10 −9 mol•cm −2 , as a low-cost, stable, and highperformance molecular electrocatalyst for selective electrochemical reduction of Cr(VI) species in pH 2 HCL/KCl. The new electrode material was characterized using SEM, FTIR, Raman, GC-MS, 1 H NMR (active site isolated as an ethanolic extract), and scanning electrochemical microscopy (SECM) techniques. It has been revealed that an intermediate electrochemical oxygen reduction reaction to H 2 O 2 occurred at CNF@Binol ads , which is a key step for the surface-adsorbed Binol-precursor oxidation to redox-active molecular electrocatalyst. CNF@Binol-Redox showed a high-performance reduction reaction at a reduction potential of 0.5 V versus Ag/AgCl (low overpotential, η = 0.5 V), which is much better than that of several conducting polymers and Pd-based electrocatalysts (high η = 1.5−0.6 V) and closer to the performance of a bulk gold electrode system. Further, this new electrode does not show any dissolved oxygen interference or surface-fouling problem. The Andrieux-Savent electrochemical kinetic model was adopted to calculate the heterogeneous rate constant (k chem ) as 4.29 × 10 5 mol −1 •dm 3 •s −1 . As practical applications, a prototype electrochemical Cr(VI) sensor operatable by one-drop analysis and bulk electrochemical detoxification of Cr(VI) to Cr(III) have been successfully demonstrated.