Generally, amines form protonated cations ([M + H]In this work, the binary ionization behavior of LCAs was reported and studied. Internal factors (functional groups and sizes of conjugated systems) and external factors (solvent type, flow rate, and electrode position) were systematically investigated and discussed.For the internal factors, electron-donating groups and large conjugated structures of LCAs were conducive to the generation of MThe present study illustrated that the formations of M