Unstable Sn(III) intermediates generated in the Sn(IV)/Sn(II) redox reaction in 2 M HBr + 4 M NaBr media were detected by scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). In CV, the underpotential deposition of Sn(0) and its stripping peaks severely perturbed the analysis of diffusional reactions. In SECM, however, the detection of diffusional Sn(III) bromide species was clearly observed due to the absence of the perturbation from the surface reactions. The ECEC-DISP mechanism in both the reduction and oxidation reactions was proposed via Sn(III) bromide intermediates. CVs at different concentrations of Sn(IV) and at various scan rates were fit by numerical simulations based on the proposed mechanism with good agreement. Enhanced electrochemical reversibility in the Sn(IV)/Sn(II) redox reaction was observed at the elevated temperature of 80 °C. We attributed such observation to changes in the rate of bromide loss from Sn(IV)Br₆²⁻ to Sn(IV)Br₅⁻ based on the CV simulation. In a similar approach, a short-lived intermediate, presumably bromine anion radical Br₂⁻·, was detected in the Br⁻ /Br₃⁻ electro-oxidation reaction in nitrobenzene solution by SECM and CV. The reaction mechanism was proposed based on a detected Br₂⁻· intermediate as follows: (1) the one electron transfer of Br⁻ to Br·, (2) the dimerization of 2Br· to Br₂, (3) the bromide addition reaction of Br₂ to Br₃⁻ , (4) the bromide addition reaction of Br· to Br₂⁻·, and (5) the Br· addition reaction of Br₂⁻· to Br₃⁻. The simulation based on the proposed mechanism fitted well with the experimental SECM and CV results. At last, the applicability of the Sn/Br system as electrolyte for electrochemical energy storage was tested. A redox flow battery was constructed, where the Sn(IV)/Sn(II) reduction was carried out on the negative electrode, while the Br· /Br₂ oxidation was carried out on the positive electrode during charging. Cyclability was tested up to 35 charge/discharge cycles, and 100 % coulombic efficiency was observed in all cycles. However, only 40 % of voltage efficiency was obtained, mainly due to the large irreversibility of the Sn(IV)/Sn(II) redox reaction in the bromide media.