The peroxide value (PV) is an important indicator to assess quality of edible oils. However, traditional methods for determining PV are complicated for operating and lack sensitivity. In this paper, we report a fast, reusable, selective and sensitive room-temperature phosphorescence (RTP)-based sensor to determine the PV of edible oils. The sensor comprises a lead-based metal–organic framework (Pb-MOF, Pb4O(TPA)3, TPA: (terephthalic acid). Luminescence studies reveal that bright RTP of Pb-MOF quenched significantly by iodide ions (I−), a classic reductant for peroxides in edible oils, thus the determination of the PV is possible. Crucially, the proposed method yields responses within 10 min and has a wide linear range of 0.35–25.62 mmol/kg, a low detection limit of 30 μmol/kg, and high selectivity for PV detection. The sensing system was successfully applied to determine the PVs of edible oils and monitor the PV of rapeseed oil during storage.