As a unconventional oil, perilla oil is much more expensive than conventional oils since it has the highest content of α-linolenic acid among vegetable oils. Thus the adulteration of perilla oil is serious, which needs to be solved. In this study, the single component oil in perilla oil blends were first quantitatively analyzed by ultraviolet–visible (UV–vis) spectroscopy combined with chemometric methods. Soybean oil and palm oil were added into perilla oil to form binary and ternary perilla oil blends. Partial least squares (PLS), back propagation-artificial neural network (BP-ANN), support vector regression (SVR) and extreme learning machine (ELM) were compared and the best model was selected for calibration. In order to improve the prediction performance of the calibration model, ten preprocessing methods and five variable selection methods were investigated. Results show that PLS was the best calibration method for binary and ternary perilla oil blends. For binary perilla oil blends, the correlation coefficients of prediction (Rp) obtained by PLS were both above 0.99, which does not need preprocessing and variable selection. For ternary perilla oil blends, after the best continuous wavelet transform (CWT) preprocessing and discretized whale optimization algorithm (WOA) variable selection, the Rp values obtained by the best model CWT-WOA-PLS were all above 0.97. This research provides a common framework for calibration of perilla oil blends, which maybe a promising method for quality control of perilla oil in industry.