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A hybrid polymeric coating (PDMS–CNPrTEOS) with sorbent properties was prepared by the sol–gel method from hydroxyl-terminated poly(dimethylsiloxane) (OH-PDMS), and cyanopropyltriethoxysilane (CNPrTEOS) as an inorganic precursor, using trifluoroacetic acid (TFA) as a catalyst. A coating with the sol–gel solution was prepared on glass plates using the dip-coating method and subsequently characterized. Characterization by FTIR shows that cyano groups are present on the surface coating and contact angle tests show that the coating presents hydrophilic characteristics. The organic–inorganic polymer was stable up to 400 °C with a weight loss of 8 wt % and showed good stability after immersion for 60 min in vortex and 45 min in ultrasonic bath, in various solvents: water, methanol (MeOH), acetone, isooctane, ethyl acetate (AcOEt) and acetonitrile (ACN), and solutions at different pH (1–12) for 48 h (h). The PDMS–CNPrTEOS hybrid polymer was evaluated and was found to have the ability to extract simultaneously furanic compounds in aqueous solution when it is employed as a sorbent for stir bar sorptive extraction (SBSE).