A novel peroxyoxalate chemiluminescence system has been designed for the determination of Triton X-100 (TX-100), in which a hydrophobic fluorescent conjugated polymer, poly[2,5-bisnonyloxy-1,4-phenyleneethynylene-9,10-anthrylene] (PPEA) was employed as a fluorophor. A strong enhanced intensity of chemiluminescence (CL) was observed in the presence of TX-100, due to the improved emission efficiency of PPEA in the presence of TX-100. Under optimum conditions, the detection range of Triton X-100 is between 1.0×10 -7 and 1.0× 10 -4 mol•L -1 , with a detection limit at 6.0×10 -8 mol•L -1 . The relative standard deviation is 2.4% (n=6) for 1.0×10 -6 mol•L -1 Triton X-100. This method provides satisfying results in the detection of TX-100 in nature water and biological samples with high sensitivity and wide linear range.