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Activationless outer‐sphere electron transfer (ET) in polar solvents is studied using the stochastic Liouville equation (SLE) formalism. The role of the initial conditions on the dynamics of activationless ET is explored. A solution of the SLE for arbitrary initial conditions is presented. Numerical results for the total population in the initial state for the equilibrium initial conditions and for the localized initial conditions are compared with approximate analytic solutions for activationless ET. For the equilibrium initial condition the approximate solution constitutes an excellent description of the ET dynamics over a broad time domain. For the initially localized state the ET dynamics exhibits sequential thermalization and activationless ET.