The solvent reorientation dynamics of the intramolecular charge-transfer (ICT) process of the (p-cyanophenyl)pentamethyldisilane—H₂O (CPDS—H2O) cluster was investigated by transient infrared (IR) absorption spectroscopy. Transient IR bands of two distinct charge-transfer (CT) states appeared in both the OH and the CN-stretching vibration regions. Analyses of the IR spectra and the time profiles of the transient bands revealed that the ICT process of the CPDS—H₂O cluster proceeds in two steps. The first step is a transition from a photo-prepared locally excited (LE) state to the CT state, which is accompanied by a minor reorientation of the H₂O moiety. In contrast, the second step is an extensive reorientation process of the H₂O molecule in the CT state. These two reorientation processes exhibit very distinct pico- and nano-second time scales. In the latter case, a relatively slow time constant of 2 ns was related to a large geometric change in the orientation.