Fluorescence organic matters contain the information about total amount and components of organic substances and could be treated as a novel water quality parameter to make up the ambiguity of COD and BOD about the pollutant composition. Refinery wastewater is a type of nonbiodegradable industrial wastewater containing a large number of toxic pollutants. The investigation on the excitation-emission matrixes of the wastewater from a large-scale refinery plant indicated that the matrix was unique for each sample; the fluorescence was intensive and was derived from the overlaps of fluorescence related to peaks at around λex/λem=270/300 nm, 220/300 nm and 230/350 nm. The intensity of 270/300 nm was the highest and that of 220/300 nm was the secondly highest. The location and intensities of peaks varied within small ranges. The fluorescence of the refinery wastewater contains information about products and raw materials. Phenol significantly contributed to the fluorescence intensity of 270/300 nm and 220/300 nm, and other compounds with one benzene ring such as dichlorobenzene and benzene contributed to the two peaks too. The fluorescence of 230/350 nm would be closely related to alkane and benzene. The location and intensity of peaks would be used to diagnose if the performance of the manufacturing processes and influent of treatment plant is proper.