Postcolumn derivatization reactions can be used to improve detector sensitivity or selectivity. The advantages of capillary chromatography for trace analysis could be augmented if there were postcolumn reactors suitable for microchromatographic systems. However, postcolumn derivatization is a challenge because of the small peak volumes associated with capillary columns. We have developed a postcolumn flow reactor from microchannels formed in fluorinated ethylene propylene and 50-μm fused-silica tubing for use with capillary HPLC analyses. Theoretical and experimental evidence show that the reactor, which operates in the Taylor dispersion regime, enables contact of analyte and derivatization streams purely by diffusion. Reactor lengths as short as 2 cm allow formation of copper(II)–peptide complexes that are detected electrochemically at a carbon fiber microelectrode. The reactor has been used with 100-μm-i.d. columns with insignificant effects (i.e., <3%) on peak band spreading. Theoretical calculations indicate that even smaller i.d. columns can be used with little effect on chromatographic resolution.