Herein we report that the reactions of potassium ferrate (VI) with a number of reductants can produce strong chemiluminescence (CL) in acidic aqueous solution. The CL Spectra were registered and compared with the classical KMnO4 and NaClO-H2O2 CL systems. The characteristic emission peaks at 1268 and 1050 nm were observed, which are consistent to the spectrum obtained from the NaClO-H2O2 system. Additional emission bands at 680 nm further confirmed the formation of singlet oxygen dimers. The high CL intensity and the chemically green nature of K2FeO4, prompt us to further develop it as a novel CL reagent. Sensitive response and wide calibration ranges were obtained for dopamine, ascorbic acid, and ethanol. The linear range for the determination of three analytes were 50 nM to 50 μM for dopamine (LOD: 20 nM), 5.0 μM to 1.0 mM for ascorbic acid (LOD: 2.21 μM), and 0.5 μM to 1.0 mM for ethanol (LOD: 0.30 μM). Thus, K2FeO4 has a great potential for the postcolumn detection of those UV featureless compounds.