Photoelectric dual-function features in bulk crystals or flexible thin films make them excellent candidates for important and thriving applications in storage, sensing and other information fields. Based on superior advantages such as easy and environmentally friendly processing, mechanical flexibility, and ability to fabricate films and bulk single crystals; we designed a type of molecular material with a photoelectric multi-function switch, [N(NH₂CH₂CH₂)₃]₂Mn₂Cl₁₂ (compound 1), which exhibits intriguing temperature-dependent dielectric and red emission switchable characteristics. This material perfectly explains the advantages of molecular materials, while 1 can also be used to fabricate a transparent unidirectional film with ultra-flexibility. Moreover, this material shows the highest record in signal contrast of ∼5 (exceeding all the known molecular materials/crystalline switches, revealing its potential to obtain high-efficiency signal-to-noise ratio), sensitive dielectric bi-stability, and excellent switching anti fatigue. These features give it a high application value in integrated circuits, optoelectronic seamless integration devices and flexible multifunctional devices.