The effects of high intensity microwave radiation in electrochemistry are summarized and discussed. In situ microwave activation of electrochemical processes has been introduced recently and is possible by placing a carefully designed electrochemical cell directly into a microwave cavity. Self-focusing of intense microwave radiation occurs into a region close to the electrode I solution (electrolyte) interface of a microelectrode placed into the electrochemical cell. The electrode diameter and the electrode material strongly affect the observed mass transport enhancement and temperature effects. Experiments have been conducted to determine the temperature at the electrode surface electrochemically and to quantify the rate of chemical processes which occur in the vicinity of the electrode under high intensity microwave conditions. The effects of microwaves in a wide range of solvent systems from aqueous solutions to organic solvents (DMSO, acetonitrile, DMF, formamide) and in an ionic liquid (BMIM+PF6-) have been investigated. Considerable current and temperature enhancements are observed in all solvents and are explained based on the interaction of microwaves with the liquid (electrolyte) and the physical properties of the liquids or solutions. (c) 2005 Elsevier Ltd. All rights reserved.