The electrooxidative and -reductive methods for the surface modification of carbon fiber were developed. The carbon fiber surface was first oxidized under anodic conditions to introduce phenolic hydroxyl groups on the carbon fiber, and then the resulting oxidized carbon fiber was treated under cathodic conditions in the presence of various kinds of electrophiles such as alkyl halides and alkyl tosylates introducing the alkyl groups on the carbon fiber. The changes of the functional groups on the carbon fibers were confirmed by the X-ray photoelectron spectroscopy (XPS) study and the observation of the hydrophilicity. The functional carbon fiber electrode introduced beta-cyclodextrin (beta-CD) was then prepared by this electrochemical method. The electroreduction of acetophenone (1) was carried out using the resulting carbon fibers as cathodes. The use of the carbon fiber modified with beta-CD gave relatively high dl selectivity of the reductive coupling products 2 (the dl/meso ratio: 5.2), while the dl/meso ratio using the untreated carbon fiber was 3.0, and the formation of 1-phenyl ethanol (3) was observed only by using the beta-CD-modified carbon fiber. The observed products selectivity is discussed from the viewpoints of the interaction between the electrogenerated species and the functional groups on the carbon fibers. (C) 2005 Elsevier Ltd. All rights reserved.