In the present paper, we present a simple, reliable, selective and sensitive method for the identification and quantification of volatile thiols at trace levels in coffee brews. A simultaneous derivatization/extraction procedure followed by liquid chromatography–electrospray high-resolution mass spectrometry is proposed and adapted to coffee brew matrix, and the performance of the method is evaluated. The linearity, sensitivity, recovery and both the intra-day and inter-day accuracy were all satisfactory. According to established identification criteria, seven target and nine non-target thiols were identified and quantified in coffee brew samples. Several of them are reported here for the first time in coffee brews, and our results are in agreement with previously reported results for coffee powder analyzed using similar analytical approach.