Anomalous enhancement of stimulated Raman scattering (SRS) derived from the OH stretching vibration of interfacial water molecules is observed when excess electrons are generated at an air/water interface by focusing an intense pulsed beam under a total internal reflection configuration. The characteristic SRS peak appears at 3200 cm(-1) and is attributed to the water molecules being in an ice-like hydrogen-bonding environment at the interface. The mechanism of the SRS enhancement is discussed in terms of the enhancement of the nonlinear polarizability of the interfacial water by the large electrostatic fields induced by the transiently generated excess electrons at the interface. (C) 2002 Published by Elsevier Science B.V.