© 2022 by the authors. Licensee MDPI, Basel, Switzerland.In this work, metal organic frameworks (A100 Al-based MOFs) were used in dispersive solid-phase microextraction (DSPME) for the isolation and preconcentration of the carbaryl from vegetable, fruit and water samples. The A100 Al-based MOFs showed excellent behavior for the adsorption of carbaryl from a water–ethanol solution; additionally, carbaryl was easily desorbed with ethyl acetate for detection by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-TMS). The analytical process of DSPME together with UPLC-TMS provides the accurate monitoring of trace carbaryl residues. The results show that the optimal recovery% of carbaryl was obtained at a sample apparent pH of 5, with the application of 1 mL of ethyl acetate to elute the carbaryl from the A100 Al-based MOFs. The limit of detection (LOD) and the limit of quantification (LOQ) were 0.01 mg.L−1 and 0.03 mg.L−1, respectively. The RSD% was 0.8–1.9, and the preconcentration factor was 45. DSPME and UPLC-TMS were successfully used for the isolation and detection of carbaryl in food and water samples.