An on-line multichannel Raman spectroscopic detection system for capillary electrophoresis was established by using an Ar+ laser and a cryogenically cooled ICCD. Resonant excitation Raman spectra of methyl red and methyl orange were employed to test the system. The result shows that it could yield on-line electrophoretogram and time series of Raman spectra. An on-line multichannel Raman spectroscopic detection system for capillary electrophoresis was established by using an Ar + laser and a cryogenically cooled ICCD. Resonant excitation Raman spectra of methyl red and methyl orange were employed to test the system. -line electrophoretogram and time series of Raman spectra.