Two modes of stepwise gradient elution of capillary electrochromatography were developed for the analysis of environmental samples on both a laboratory-made and a commercial CE instrument. Using the laboratory-made apparatus, another mobile phase was dropped directly into the inlet vial with a pipet. By this means, nine 2,4-dinitrophenylhydrazine (DNPH)-derivatized ketones and aldehydes were separated with high resolution. Not only was analysis time shortened by more than one half, but the detection limit was greatly improved compared to that in isocratic elution. The latter was achieved using the P/ACE 5510 system (Beckman Instruments, Fullerton, CA, U.S.A.), which moved the mobile phase vials automatically. The stop-flow technique was utilized during transfer. It had no effect on solute retention. With this method, the concentration and type of organic modifier in the mobile phase could be changed. A mixture of 13 aromatic hydrocarbons was separated completely in 14 min by changing the mobile phase from 80% methanol to 80% acetonitrile and 90% acetonitrile in a sequential step mode. The RSD of the retention time of each component in six consecutive injections was below 0.374%. All of these results demonstrate that stepwise gradient elution of capillary electrochromatography may be useful in the analysis of complex environmental samples.