A supramolecular solvent consisting of vesicles, made up of equimolecular amounts of decanoic acid (DeA) and tetrabutylammonium decanoate (Bu 4NDe), dispersed in a continuous aqueous phase, is proposed for the extraction of benzimidazolic fungicides (BFs) from fruits and vegetables. Carbendazim (CB), thiabendazole (TB) and fuberidazole (FB) were extracted in a single step and no clean-up or concentration of extracts was needed. The high extraction efficiency obtained for BFs was a result of the different types of interactions provided by the supramolecular solvent (e.g. hydrophobic and hydrogen bonds) and the high number of solubilisation sites it contains. Besides simple and efficient, the proposed extraction approach was rapid, low-cost, environment friendly and it was implemented using conventional lab equipments. The target analytes were determined in the supramolecular extract by LC/fluorescence detection. They were separated in a Kromasil C 18 (5 μm, 150 mm × 4.6 mm) column using isocratic elution mobile phase: 60:40 (v/v) 50 mM phosphate buffer (pH 4)/methanol and quantified at 286/320 nm (CB) and 300/350 nm (TB and FB) excitation/emission wavelengths, respectively. Quantitation limits provided by the supramolecular solvent-based microextraction (SUSME)/LC/fluorescence detection proposed method for the determination of CB, TB and FB in fruits and vegetables were 14.0, 1.3 and 0.03 μg kg −1, respectively, values far below the current maximum residue levels (MRLs) established by the European Union, i.e. 100–2000 μg kg −1 for CB, 50–5000 μg kg −1 for TB and 50 μg kg −1 for FB. The precision of the method, expressed as relative standard deviation, for inter-day measurements ( n = 13) was 3.3% for CB (50 μg kg −1), 3.5% for TB (10 μg kg −1) and 2.8% for FB (0.5 μg kg −1) and recoveries for fruits (oranges, tangerines, lemons, limes, grapefruits, apples, pears and bananas) and vegetables (potatoes and lettuces) fortified at the μg kg −1 level were in the interval 93–102%.