AbstractWith the flourishing development of star molecule (CH₃NH₃)PbI₃, organic-inorganic perovskites with multifunction and flexibility have become a worldwide focus. However, the controllable photoelectric switchable material (especially electric, optical, thermal multifunctional switches) still face great challenges, and most of them are ceramic and toxic lead-based series. Herein a lead-free perovskite-like crystal and flexible thin film, ImMC (ImMC = (HIm)₆∙[MnCl₄∙MnCl₆]) (1), with many advantages over inorganic ceramics and lead-based perovskites, performs ideal optical and dielectric duple switching properties simultaneously. The order-disordered HIm (Im = imidazole) cations of α-type occupy two lattice sites corresponding to “Switch-ON/0” and “Switch-OFF/1” states, respectively. Interestingly, the optical and dielectric “ON/OFF or 0/1” switches can be integrated into one single-molecule single/duple channel module with high signal-noise ratio, in which the “ON/OFF” response can be precisely controlled by temperature or/and light wavelength signal to realize automatically multiple switching. In brief, the lead-free multifunctional switch opens up a brand new route and shows the mark of its real genius as a highly desirable material for its advanced applications in highly integrated circuit and ultrahigh-encrypted storage in flexible photoelectric devices.