External stimuli can alter the physical properties of materials during phase transitions in the solid state. Many researchers have investigated the influence of external stimuli on magnetic, electrical, and optical properties. For example, we previously revealed switching phenomena in cyano-bridged metal complexes induced by various external stimuli. Herein, we introduce how the functionalities of rubidium manganese hexacyanoferrate are driven by a thermally induced and photoinduced charge transfer coupled with structural phase transitions. Understanding how photoinduced phenomena and functions emerge is a great challenge of current interest and new ultrafast techniques, sensitive to electronic and/or structural degrees of freedom, open a nice opportunity for understanding and controlling materials at work.