A method has been developed for photometric detection of cyclodextrins (CD) in liquid chromatography using iodine (I2) generated electrochemically in-situ. Iodide ion in the mobile phase was electrochemically oxidized to I2 which was subsequently reacted with I-, in an electrochemical flow cell, forming I3-. The absorbance of I3- was found to be greatly enhanced when CD were present in the mobile phase. The absorbance enhancement was caused by the change in the mole fraction of I3-, because of the inclusion reaction of I3- with CD. On the basis of this phenomenon, CD were detected by means of a photodiode-array UV-visible detector positioned downstream of the electrochemical flow cell. The signals were found to be linearly dependent on CD concentration. Because the formation constants of I3- with CD decrease in the order alpha-CD>beta-CD>gamma-CD, alpha-CD was most detectable by the method. Detection limits were 1.0 micromol L(-1) for alpha-CD, 65 micromol L(-1) for monoG1-beta-CD, 100 micromol L(-1) for beta-CD, and 200 micromol L(-1) for gamma-CD.