The polymer-assisted reaction of 4-(hydroxymethyl)furan-2(5H)-one (4HM2F) with 21 carboxylic acids using polystyrene-carbodiimide (PS-carbodiimide) yielded an ester library. Four of the esters, (5-oxo-2,5-dihydrofuran-3-yl)methyl acetate (IS-1), (5-oxo-2,5-dihydrofuran-3-yl)methyl butyrate (IS-2), (5-oxo-2,5-dihydrofuran-3-yl)methyl 2-methylpropanoate (IS-3), and (5-oxo-2,5-dihydrofuran-3-yl)methyl chloroacetate (IS-4), were tested as internal standards for the quantification of patulin in apple juice by gas chromatography-mass spectrometry in the selected ion monitoring mode (GC-MS-SIM). The developed method combines an AOAC official extractive step and a GC-MS-SIM analysis. Using a chromatographic column containing trifluoropropylmethylpolysiloxane as the stationary phase and IS-1 as the internal standard, it was possible to perform an accurate and precise quantification of underivatizated patulin in apple juice at concentrations down to 6 microg/L. A detection limit of 1 microg/L was established.