A review of the basic aspects of fluorescence line-narrowing spectroscopy (FLNS) and its coupling with thin-layer chromatography (TLC) and polyacrylamide gel electrophoresis (PAGE) for off-line high-resolution low temperature spectral characterization is discussed. This is followed by a description of the on-line interfacing of capillary electrophoresis (CE) and capillary electrochromatography (CEC) with FLN detection. CE/CEC-FLNS instrumentation and its applications for spectral identification of closely related analytes are also presented. Future prospects of micro and capillary high performance liquid chromatography (HPLC) with on-line high-resolution low temperature spectroscopic identification are considered.