We report the utilization of a high power ultraviolet light emitting diode for fluorescence detection (UV-LED-IF) in capillary electrophoresis (CE) separations. CE-UV-LED-IF allows analysis of a range of environmentally and biologically important compounds, including polyaromatic hydrocarbons (PAHs) and biogenic amines, including neurotransmitters, amino acids, proteins and peptides, that have been derivatized with UV-excited fluorogenic labels, e.g. o-phthaldialdehyde/β-mercaptoethanol (OPA/β-ME). The 365 nm UV-LED was used as a stable, low cost source for detection of UV-excited fluorescent compounds. UV-LED-IF was used with both zonal CE separations and micellar electrokinetic chromatography (MEKC). Native fluorescence detection of PAHs was accomplished with detection limits ranging from 10 nM to 1.3 µM. Low-nM detection limits for OPA/β-ME-labeled amino acids were achieved for both online and offline analysis, comparable to UV-laser based systems. Analysis of OPA/β-ME-labeled proteins and peptides was also performed with high sensitivity. Here, we present potential of these devices in miniaturized microfluidic systems for online chemical monitoring applications, as well as for the construction of low-cost CE systems for routine laboratory use.