Photoelectron spectra (PESs) of Li-(NH3)(n) (n less than or equal to 16), Na-(NH3)(n) (n less than or equal to 12), and Na-(H2O)(n) (n less than or equal to 7), as well as the ionization potentials (IPs) of Li(NH3)(n), (n less than or equal to 28) and Li(H2O)(n) (n less than or equal to 46), are examined. PESs of Li-(NH3)(n) (n less than or equal to 10) exhibit three bands derived from the Li(3(2)S)-Li-(S-1), Li(2(2)P)-Li-(S-1), and Li(2(2)S)-Li-(S-1) transitions. The vertical detachment energies of the 3(2)S- and 2(2)P-type states decrease dramatically with increasing n. For n greater than or equal to 11, the transitions to the 2(2)P- and 3(2)S-type states almost. become degenerate with the transition of the neutral ground (2(2)S) state. In addition to these observations, we also find the red shift of rile 2(2)S-type transition with a much slower rate. The similar spectral trends are also observed for the Na(3(2)P)-Na-(S-1) and Na(3(2)S)-Na-(S-1) transitions of Na-(NH3)(n). On the other hand, the transitions of Na-(H2O)(n) exhibit the opposite shifts, and the P-2-S-2 energy separation does not change. As for Li(H2O)n, we find a monotonous decrease in IPs with n less than or equal to 4 and a constant IP behavior for n greater than or equal to 5. The limiting value for n --> infinity (3.12 eV) is comparable to the estimated photoelectric threshold of ice as in the case of Cs(H2O)(n) reported previously. On the basis of these results as well as those of the ab initio calculations, we discuss the early stage of solvated-electron formation in finite clusters.