Upon photoexcitation of the charge-transfer-to-solvent absorption band of Na- in tetrahydrofuran (THF), electrons detach into immediate contact pairs, solvent-separated contact pairs, or as free electrons. In this Letter, we analyze the recombination dynamics of Na- at multiple excitation wavelengths to determine the action spectrum for production of each type of electron. The action spectra match well with the four Gaussian sub-bands (corresponding to three p-like CTTS states and the continuum) needed to describe the polarized bleach recovery. We also find that the Na- free-electron action spectrum is linearly related to the Rb-/THF photocurrent action spectrum measured by Levanon and co-workers. (C) 2003 Elsevier Science B.V. All rights reserved.