Ultrafast spectroscopy has been used to study the relaxation processes of charge carriers in ZnO nanocrystalline thin films. A broad red-IR absorption band linked to shallowly trapped electrons was observed by spectroelectrochemical measurements. Femtosecond transient absorption data revealed multiexponential decays of the charge carriers with time constants ranging from 1 to 400 ps. The decay profile of the signal shows a probe wavelength dependence. This effect is assigned to the trapping (localisation) of nonequilibrium charge carriers which occurs on a time scale of similar to1 ps. The recombination of shallowly trapped electrons with deeply trapped holes, determined by single-photon counting, mainly occurs in 400 ps. (C) 2004 Elsevier B.V. All rights reserved.