Flash photolysis of K−, Rb−, and Cs−in tetrahydrofuran (THF) produces the corresponding ion-pairs (K+, es−), (Rb+, es−), and (Cs+, es−), followed by the regeneration of the parent metal anion, M−. In mixed-metal solutions containing Na and M where M is K, Rb, or Cs, photolysis of Na−also forms the (M+, es−) ion-pair and M−, but with the latter then reforming Na−on an extended time scale. Similar results were obtained in dimethoxyethane (DME) at 213 K, but in this case with the initial formation of a loose ion-pair, (M+, es−)loose.Based on a Gaussian–Lorenztian shape function, the 'best-fit' optical bands for the (M+, es−) and M−species were used to simulate the experimental spectra and deduce the corresponding extinction coefficients in both solvents.The overall mechanism is complex but is in good agreement with previous interpretations deduced by pulse radiolysis.