An efficient and practical method for identifying mandarin juice over-blended into not from concentrate (NFC) orange juice was established. Juices were extracted from different cultivars of sweet orange and mandarin fruits. After being pasteurized, the volatile organic compounds (VOCs) in the juice samples were extracted using headspace solid-phase microextraction, and qualitatively and quantitatively analyzed using gas chromatography–mass spectrometry detection. Thirty-two VOCs contained in both the sweet orange juice and mandarin juice were used as variables, and the identification model for discriminating between the two varieties of juice was established by principal component analysis. Validation was applied by using common mandarin juices from Ponkan, Satsuma and Nanfengmiju cultivars blended at series of proportions into orange juices from Long-leaf, Olinda, and Hamlin cultivars. The model can visually identify a blending of mandarin juice at the volume fraction of 10% or above.