A new polymeric sorbent synthesised by exploiting molecular imprinting technology has been used to selectively extract naphthalene sulfonates (NSs) directly from aqueous samples. In the non-covalent molecular imprinting approach used to prepare this polymer, 1-naphthalene sulfonic acid (1-NS) and 4-vinylpyridine (4-VP) were used as a template molecule and functional monomer, respectively, and both dissolved in a mixture of methanol/water (4:1) as porogen together with the cross-linker ethylene glycol dimethacrylate. The new non-covalent molecularly imprinted polymer (MIP) prepared in aqueous environment was used as a sorbent in solid-phase extraction (SPE) to selectively extract a group of naphthalene mono- and disulfonates. When one litre of a standard aqueous solution, which contained a mixture of eight NSs, was percolated through the SPE cartridge, all the NSs were retained on the MIP because of the cross-reactivity of the polymer. Recoveries were higher than 80% for all the compounds even after a clean-up step with methanol (MeOH). The MIP was also used to analyse water from the Ebro river.