The absorption spectra of Li-H2O and Li-D2O, produced by the laser vaporization technique, are examined in the energy region of 10300-11700 cm(-1) using a photodepletion method. Vibrationally resolved bands beginning at energies of 10464 and 10525 cm(-1) are observed for Li-H2O and Li-D2O, respectively. These peaks are assigned to the transition from the 1(2)A(l) ground state to the 2(2)A(l) excited state correlating to Li(P-2) + H2O((1)A(1)). This transition is more than 4000 cm(-1) to the red of the Li ((2)p-S-2) atomic transition. The extensive redshift of the 2(2)A(1)-1(2)A(1) transition is ascribed to the large increase in ionic character in the upper state due to partial electron transfer. The spectrum of the Li-H2O complex exhibits two extra vibronic bands in the region of 300-500 cm(-1) above the origin. These bands are tentatively ascribed to the transitions as a result of vibronic interaction between the low-lying excited states.