Crosslinkers are indispensable constituents for the preparation of SPE materials with ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) among the most prominent representatives. A crosslinker that has not yet been used for the preparation of SPE sorbents is 3,3’-(hexane-1,6-diyl)bis(1-vinylimidazolium) bromide [C6-bis-VIM] [Br]. In this study, we synthesized differently crosslinked vinylimidazole polymers with EGDMA, DVB and [C6-bis-VIM] [Br] and evaluated their extraction efficiencies towards phenolic acids. Dispersive SPE experiments performed with the [C6-bis-VIM] [Br] crosslinked polymers exhibited significantly higher extraction recoveries for the majority of analytes. Due to these promising results, the [C6-bis-VIM] [Br] crosslinked polymer was optimized in terms of the monomer to crosslinker ratio and an efficient dispersive SPE protocol was developed, with maximum recoveries ranging from 84.1–92.5% and RSD values ˂ 1%. The developed extraction procedure was also applied to cartridges resulting in recoveries between 97.2 and 98.5%, which were on average 5% higher than with the commercial anion exchange sorbent Oasis® MAX. Furthermore, the sorbent was regenerated showing a good reusability for the majority of analytes. In conclusion, this study clearly highlights the yet untapped potential of the crosslinker, [C6-bis-VIM] [Br], with respect to the synthesis of efficient anion exchange polymers for SPE.