A new method for the trace analysis of trans-resveratrol in wine was studied by developing a silylation on the fibre coating following solid-phase microextraction (SPME) combined with GC/MS. The silylation was performed directly by placing the fibre into the headspace of silylating reagent. The method is rapid and sensitive without going through laborious sample preparation. The effects of fibre selection, extraction and desorption times as well as the extraction temperature were studied. The optimum conditions of derivatization time and temperature were also studied. The derivatization was carried out at room temperature without damaging the fibre coating. A linear response of trans-resveratrol over a concentration range of 10ngl−1–1mgl−1 with a correlation coefficient of 0.9997 and detection limit 5ngl−1 (3s criteria) were obtained. The analytical recoveries in wine ranged from 84 to 106% with precision below 10% relative standard deviation (R.S.D.).