Triphenylmethylium cation catalyzed Povarov reactions with excellent yields in 1 h with a remarkably low loading (0.5 mol %) are disclosed. A Lewis acidic carbenium catalysis mechanism was proposed and validated. A three-component Povarov reaction in a batch was transferred into a two-stage microflow process, which resulted in a 60-fold reduction in reaction time from 2 h to 2 min with 89% separated yield.