Sorbent polymers can be designed to target molecular interactions with a variety of hazardous chemicals including explosives, chemical agents, narcotics, and toxic industrial chemicals. Applications of functionalized sorbent polymers include preconcentrator devices, SPME fibers, membrane introduction systems, chromatographic stationary phases and coatings for chemical sensors. One common feature of a wide range of hazardous chemicals is their hydrogen bond (h-b) basicity. In this work, we report on the synthesis and characterization of a h-b acidic hyperbranched carbosilane fluoroalcohol based sorbent polymer (poly(methyldi(1,1,1-trifluoro-2-trifluoromethyl-2-hydroxypent-4-enyl)si lane; HCSFA2), which is suitable for sorbing these hazardous h-b basic analytes. Multiple batches of HCSFA2 were characterized with routine composition, spectroscopic, thermal analysis, and inverse gas chromatography (iGC) to evaluate polymer physicochemical properties. In comparison with previously developed h-b acidic polymers (e.g., FPOL and SXFA), HCSFA2 exhibits a sorption improvement of 10-15 fold for h-b basic analytes. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3000-3009, 2010