Using femtosecond time-resolved two-photon photoelectron spectroscopy, we determine (i) the vertical binding energy (VBE = 0.8 eV) of electrons in the conduction band in supported amorphous solid water (ASW) layers, (ii) the time scale of ultrafast trapping at pre-existing sites (22 fs), and (iii) the initial VBE (1.4 eV) of solvated electrons before significant molecular reorganization sets in. Our results suggest that the excess electron dynamics prior to solvation are representative for bulk ASW.