Traditional micro-scale simultaneous distillation-extraction (SDE) and stir bar sorptive extraction (SBSE) were compared for their effectiveness in the extraction of volatile organic compounds in a synthetic grape juice and a real grape juice (Huxelrebe, a variety of half Muscat ancestry) from an English vineyard. The novel immersion-mode SBSE method, using stir bars with PDMS sorbent, was optimised using the synthetic grape juice. Although mean percent relative recoveries and reproducibilities (%CV) of the SBSE method were inferior to SDE (28.4 and 8.5%, respectively, against 86.9 and 6.3%), the former method proved to be significantly more sensitive: 126 aroma compounds in Huxelrebe grape juice were identified using SBSE, against 98 using SDE. This allowed the identification of a number of volatile components that have not been reported previously in the juice or wine from the grapes of Muscat varieties.