Abstract: A rapid fluorometric method was established to detect glyphosate by using cerium ion and pyrophosphate ion (Ce-PPi) coordination polymer networks (CPNs). Based on coordination of cerium ion (Ce³⁺) and pyrophosphate ion (PPi), fluorescent Ce-PPi CPNs were synthesized by simple self-assemble process, and the structure and properties were characterized. Upon introducing glyphosate, the ligand field effect of PPi with Ce³⁺ was weakened resulting in a decrease in fluorescence of Ce-PPi CPNs. Based on this principle, the quantitative detection of glyphosate was achieved by optimizing the conditions, with R² of 0.9972 and the detection limit of 0.014 μmol/L. The established method based on Ce-PPi CPNs possessed outstanding sensitivity and exclusive selectivity for rapid detction of glyphosate, and could be used for the detection of glyphosate in tap water and apple samples. The limit of quantitation (LOQ) was 0.05 mg/kg and the recoveries were between 77% and 87%. The method provided a potential choice for the rapid, on-site and real-time, detection of glyphosate.