AbstractA rapid method for the quantitative determination of peroxide value (PV) of vegetable oils by Fourier transform infrared (FTIR) transmission spectroscopy is described. Calibration standards were prepared by the addition oft‐butyl hydroperoxide to a series of vegetable oils, along with random amounts of oleic acid and water. Additional standards were derived through the addition of mono‐ and diglyceride spectral contributions, as well as zero PV spectra obtained from deuterated oils. A partial least squares (PLS) calibration model for the prediction of PV was developed based on the spectral range 3750–3150 cm−1. Validation of the method was carried out by comparing the PV of a series of vegetable oils predicted by the PLS model to the values obtained by the American Oil Chemists Society iodometric method. The reproducibility of the FTIR method [coefficient of variation (CV)=5%)] was found to be better than that of the chemical method (CV =9%), although its accuracy was limited by the reproducibility of the chemical method. The method, as structured, makes use of a 1‐mm CaF2 flow cell to allow rapid sample handling by aspiration. The spectrometer was preprogrammed in Visual Basic to guide the operator in performing the analysis so that no knowledge of FTIR spectroscopy is required to implement the method. The method would be suitable for PV determinations in the edible oil industry and takes an average of three minutes per sample.