Two different routes for ejection of hydrated electrons by photoexcited CuCl2- and CuCl32- have been observed : (1) a prompt (i.e. within the 5-ns laser pulse width) ejection directly from the charge-transfer excited states (characterized as CTTS or Rydberg states), and (2) a delayed ejection, with lifetimes of up to 105 ns, from the triplet states of the two complexes. These tow processes have rather high quantum yields : 0.30-0.40 for the prompt ejection and 0.25-0.33 for the delayed ejection for the chlorocuprate(I) complexes. The delayed ejection process is the primary decay route for the two triplet species, (CuCl2-)-Cu-3 and (CuCl32-)-Cu-3, which are formed by intersystem crossing from the charge-transfer excited states formed by absorption of light by the bis- and triscoordinated complexes in equilibrium in the ground state. Both of the chlorocuprate triplet excited states are weakly luminescent species. The triplet tris species, (CuCl32-)-Cu-3, has a strong absorption band at 390 nm (epsilon approximate to 27 000 M-1 cm(-1)), and the biscoordinated species, (CuCl2-)-Cu-3, probably absorbs in the same region as well. Other intermediates such as Cu(0) complexes and Cl-2(.-) radicals have also been observed as decay products. Prompt and delayed electron ejection has also been observed in CuBr32- with quantum yield of 0.25 and 0.18, respectively. A mechanism that incorporates a triplet excited state equilibrium is invoked to account for these observations.