Ultrafast pump-probe spectroscopy (lambda(pump) = 420 nm) was applied to study the primary photochemical processes for IrCl62- complex in aqueous solutions. The excitation to LMCT T-2(2u) state was followed by formation of an intermediate absorption completely decaying with two characteristic times of 0.5 and 18 ps. Complete recovery of the ground state is consistent with the absence of photochemical activity of visible LMCT bands of IrCl62-. Possible interpretations of the observed two times are presented. (C) 2009 Elsevier B. V. All rights reserved.