As an important sustainable method for chemical synthesis, organic electrosynthesis experienced a renaissance in recent years for its excellent atom economy. Although microchannel reactors have been proposed to advanced electrosynthesis devices to obtain low energy cost and high reaction performance, the complex multiphasic flow in the electrochemical microchannels are very less reported and the effects of flow condition on the electrosynthesis reaction are less reported. Taking the electrosynthesis of tetraethyl thiuram disulfide (TETD) as a typical case, we developed a visualized electrochemical microchannel reactor equipped with fluorine‐doped tin oxide (FTO) loaded glass electrode to investigate the gas‐liquid‐liquid triple phase flow pattern and the main factors influenced the response current at certain applied cell voltage. The gas‐liquid‐liquid hybrid flow with low gas hold‐up and high liquid flow rate was found crucial for preventing coverage of TETD on the electrode, which provided 23.1% low current attenuation ratio at 3.0 V cell voltage. The research not only exhibited the complex evolution mechanism of the response current, but also showed the importance of flow condition control for balancing the work efficiency and energy consumption of electrosynthesis process.