Study of xenobiotics present in fruit peel by exposing it (without any pretreatment) to direct analysis in real time coupled to a high-resolution orbitrap mass spectrometer (DART-HRMS) is reported for the first time. Variables such as DART gas heater temperature and pressure, source-to-MS distance, and sample velocity are investigated. The analysis of one sample by DART-MS lasts ca. 1 min, and the benefits of both high-resolution and tandem mass spectrometry to elucidate nontarget or unknown compounds are combined. Identification of postharvest fungicides, antioxidants, and sugars in fruit peel is performed in the positive ion mode. A possible elemental formula is suggested for marker components. The lowest imazalil concentration that could be detected by this system is 1 ng (equivalent to a concentration of ca. 300 μg kg-1), which is well below the maximum residue limit. For oranges and apples, direct peel exposition demonstrated good interday precision (within 20% for any concentration) and proper linearity (R2 ≥ 0.99), with a dynamic range from 1 to 2500 ng for apple. A comparison of the results obtained using the direct peel screening DART-based method is made with those obtained by DART analysis of solvent extracts, as well as those obtained analyzing these extracts by ultrahigh-performance liquid chromatography orbitrap mass spectrometry (UHPLC-Orbitrap). The results are in good agreement. Thus, the proposed method proves to be quantitatively accurate with indisputable identification specificity. As an independent method, the approach of direct scanning of peel is of high interest and of potential future within food analysis to guarantee safety, quality, and authenticity.