Stir bar sorptive extraction (SBSE) was evaluated for analysing volatile compounds in vinegar. The extraction and desorption analytical conditions have been optimised using a two-level factorial design expanded further to a central composite design. This chemometric tool is very appropriate in screening experiments where the aim is to investigate several possibly influential and/or interacting factors. For the extraction step, the optimum analytical conditions were: sample volume 25ml without dilution, sampling time 120min, NaCl content 5.85g, and stirring speed 1250rpm. For the desorption step, the optimised analytical conditions were: desorption temperature 300°C, cryofocusing temperature −140°C, flow of helium 75mlmin −1 , and desorption time 10min. The SBSE procedure developed shows detection limits, and linear ranges adequate for analysing this type of compounds. The repeatability values obtained were lower than 10%.SBSE is a very simple, solvent-free, fast technique with better sensitivities, in general, than SPME. However, a disadvantage of this technique is that, up to now, the stir bar offers a limited enrichment capability for polar compounds because is only available with PDMS coating.