Abstract: | Electroorganic synthesis is an environmentally friendly alternative to traditional synthetic methods; however, the application of this strategy is heavily hindered by low product selectivity. Metal–organic frameworks (MOFs) exhibit high selectivity in numerous catalytic reactions; however, poor conductivity heavily limits the application of MOFs in electroorganic synthesis. To realize the electrocatalytic application of MOFs in selective electroorganic synthesis, a practically applicable strategy by suspending ion electrocatalysts in charged MOFs is herein reported. This approach could markedly improve the product selectivity in electroorganic synthesis. In the electrocatalytic oxidative self‐coupling of benzylamine experiments, the imine product selectivity is markedly improved from 61.3 to 94.9 %, when the MOF‐based electrocatalyst is used instead of the corresponding homogeneous electrocatalyst under the identical conditions. Therefore, this work opens a new route to improve the product selectivity in electroorganic synthesis. |