This is the first study aiming the discrimination of β-cyclodextrin (β-CD)/hazelnut (Corylus avellana L.) oil/antioxidant ternary complexes through Fourier-transform infrared spectroscopy coupled with principal component analysis (FTIR-PCA). These innovative materials combine the characteristics of the three components in order to enhances the properties of ternary complexes such as the onsite protection against oxidative degradation of hazelnut oil unsaturated fatty acid glycerides, increased apparent water solubility and bioaccessibility of the hazelnut oil components and antioxidants, or controlled release of bioactive compounds (fatty acid glycerides and antioxidant flavonoids, namely hesperidin, naringin, rutin and silymarin). The appropriate method for obtaining the ternary complexes was kneading at various molar ratios (1:1:1 and 3:1:1 for β-CD hydrate:hazelnut oil (average molar mass of 900 g/mol):flavonoid). Recovering yields of the ternary complexes were in the range of 51.5-85.3%, higher for 3:1:1 samples. Their thermal stability was evaluated by thermal analyses. Discrimination of the ternary complexes was easily performed through the FTIR-PCA coupled method, especially based on the stretching vibrations of CO groups in flavonoids and/or CO/CC groups in ternary complexes at 1014.6(±3.8) and 1023.2(±1.1) cm-1 along the second PCA component (PC2), respectively. The wavenumbers are more appropriate for discrimination than the corresponding intensities of the specific FTIR bands. On the other hand, ternary complexes were clearly discriminated from the starting β-CD hydrate along the first component (PC1) by all FTIR band intensities and along the PC2 by the wavenumber of the asymmetric stretching vibrations of the CH groups at 2922.9(±0.4) cm-1 for ternary complexes and 2924.8(±1.4) cm-1 for β-CD hydrate. The first two PCA components explain 70.38% from the variance of the FTIR data (from a total number of 26 variables). Other valuable classifications were obtained for the antioxidant flavonoids, with a high similarity for hesperidin and naringin, according to FTIR-PCA, as well as for ternary complexes depending on molar ratios. The FTIR-PCA coupled technique is a fast, nondestructive and cheap method for evaluation of the quality and similarity/characteristics of these new types of cyclodextrin-based ternary complexes having enhanced properties and stability and that can have applications in food supplements or functional food products.