A cyclic‐voltammetry‐based screening method for Cp2TiX‐catalyzed reactions is introduced. Our mechanism‐based approach enables the study of the influence of various additives on the electrochemically generated active catalyst Cp2TiX, which is in equilibrium with catalytically inactive [Cp2TiX2]−. Thioureas and ureas are most efficient in the generation of Cp2TiX in THF. Knowing the precise position of the equilibrium between Cp2TiX and [Cp2TiX2]− allowed us to identify reaction conditions for the bulk electrolysis of Cp2TiX2 complexes and for Cp2TiX‐catayzed radical arylations without having to carry out the reactions. Our time‐ and resource‐efficient approach is of general interest for the design of catalytic reactions that proceed in single‐electron steps.