A dual-ligand strategy was employed to construct an electrochemiluminescence (ECL) sensing platform based on dual-ligand Tb-MOF and Ag3PO4@TCPP for sensitive detection of chloramphenicol (CAP), demonstrating its potential applications in environmental monitoring and food safety. The dual-ligand Tb-MOF can be used as a co-reactant promoter, facilitating the rapid electroreduction of S2O82- to generate more oxidative mediator SO4•-, thereby enhancing the luminescence efficiency of the luminescent material Ag3PO4@TCPP. Furthermore, the integration of Ag3PO4@TCPP emitter could effectively overcome the aggregation-caused quenching (ACQ) effect of TCPP and then increase the luminescence intensity by seven-fold, which was attributed to the efficient electron transfer and energy transfer between Ag3PO4 and TCPP. Additionally, ECL spectra and electron spin resonance (ESR) spectra were utilized to investigate the possible ECL mechanism of the dual-ligand Tb-MOF/Ag3PO4@TCPP system. As a proof of concept, we successfully established an ECL biosensor for detecting CAP, which displayed a wide linear range (10-6 ~ 10-15 M) and low detection limit (8.29 × 10-16 M), demonstrating practical feasibility. This study introduces a dual-ligand strategy to enhance ECL signals, expands the application scope of dual-ligand lanthanide MOFs, and provides new insights into designing high-performance sensing platforms.