We study by femtosecond optical pump‐probe spectroscopy the photoinduced charge transfer (CT) in the RbMnFe Prussian blue analogue. Previous studies evidenced the local nature of the photoinduced MnIIIFeII → MnIIFeIII process, occurring within less than 1 ps. Here we show experimentally that two photoswitching pathways exist, depending on the excitation pump wavelength, which is confirmed by band structure calculations. Photoexcitation of α spins corresponds to the Mn(d‐d) band, which drives reverse Jahn–Teller distortion through the population of antibonding Mn‐N orbitals, and induces CT within ≈190 fs. The process launches coherent lattice torsion during the self‐trapping of the CT small‐polaron. Photoexcitation of β spins drives intervalence Fe→Mn CT towards non‐bonding states and results in a slower dynamic.