Orange fruit is one of the most popular types of fruit in the world, and its juice is the main product of its processing. This study aimed to evaluate a simple, fast, and eco-friendly methodology, atmospheric solids analysis probe mass spectrometry (ASAP-MS), to assess the chemical profile of four oranges varieties (Valencia, Folha Murcha, Pera, and Iapar). The oranges' varieties were evaluated for the physicochemical composition (extraction yield, pH, total titratable acidity, total soluble solids [TSS], °Brix), ratio (TSS/TA), and bioactive compounds (ASAP-MS analysis). The characterization of oranges resulted in great values of oranges yield according to the varieties (44.00-48.10% [w/w], adequate and characteristic acidity [0.73-1.35%], soluble solids content (10.24-13.80°Brix), pH (3.30-3.96), and ratio (7.59-19.90) level for this fruit. This powerful method showed that all analysis procedures were simple, fast, and easy because there is no need to prepare the sample and the analysis time lasted 2 min. Besides, results obtained exhibited a vast array of chemical groups. Principal component analysis (PCA) defined and distinguished the varieties of the orange. Therefore, ASAP-MS and PCA showed that they are very attractive candidates for routine analysis to monitor the varieties of the orange with its pronounced advantages, besides being contributing to the environment because it does not use any quantities of organic solvents. This methodology was applied for the first time to this type of sample.