Organophosphate flame retardants (OPFRs) are emerging contaminants that cause great concern, and triphenyl phosphate (TPHP) with an extremely serious biotoxicity is a representative harmful OPFR. It remains a great challenge to develop real-time sensing strategy for TPHP. Herein, a UV-induced chemiluminescence (CL) sensing platform with potassium monopersulfate (PMS) as the source of reactive oxygen species (ROS) is established. Extraordinary CL emission can be generated due to the oxidation of luminol by ROS (e.g., SO4− and OH) from the UV-activated PMS. More importantly, the CL emission is greatly inhibited with the introduction of TPHP. Mechanism investigation for CL inhibition effect shows that, TPHP reacts with these ROS, leading to the obvious competitive consumption of ROS, and thus the oxidation degree of luminol is significantly impaired. Based on this, a new CL platform for the sensing of TPHP is fabricated, which demonstrates the advantages of simple operation, rapid determination, miniaturization potential, high selectivity and sensitivity, and grants the limit of detection down to 42.3 ng/L. This interesting work paves the way for the fast discrimination of emerging contaminants, and exhibits great prospects in real-time environmental monitoring.