Metal–organic frameworks (MOFs) featured with flexible design and versatile properties are finding increasing applications. In particular, integrating multiple functions into one framework can bring them improved detection efficiency towards various analytes. Herein, for the first time, a Fe–Zr bi-metal–organic framework (UiO-66(Fe/Zr)-NH₂) with three functions (intrinsic fluorescence, peroxidase-mimicking activity, and specific recognition) is designed to establish a ratiometric fluorescent platform for high-performance phosphate ion (Pi) sensing. The use of a fluorescent organic ligand endows the MOF material with a strong intrinsic fluorescence at 435 nm. The presence of Fe³⁺/Fe²⁺ nodes offers good enzyme-like capacity to catalyze the o-phenylenediamine (OPD) substrate to fluorescent OPDox (555 nm), which then quenches the intrinsic fluorescence of UiO-66(Fe/Zr)-NH₂ due to the inner filter effect. The Zr⁴⁺ nodes in the MOF material act as selective sites for Pi recognition. When Pi exists, it specifically adsorbs onto UiO-66(Fe/Zr)-NH₂ and decreases the latter's peroxidase-mimetic activity, resulting in the less production of fluorescent OPDox. As a consequence, the intrinsic fluorescence of UiO-66(Fe/Zr)-NH₂ at 435 nm is restored, and the signal from OPDox at 555 nm is reduced inversely. With the ratiometric strategy, efficient determination of Pi with outstanding sensitivity and selectivity was realized, giving a detection limit down to 85 nM in the concentration range of 0.2–266.7 μM. Accurate measurement of the target in practical water matrices was also validated, indicating its promising application for Pi analysis in environmental and other fields.