Abstract A rapid X‐ray spectrometric (XRS) method has been developed for the determination of the total glucosinolate content of oilseed rape and other Brassica oilseeds. The method is based on analysis for fully oxidised sulphur (S 6+ ), which includes half the sulphur (S) in the glucosinolate molecule, and the S in sulphate. Results are highly correlated with glucosinolate content determined by glucose release, a standard method widely used in Australia. The relationship is total glucosinolates = (23·97 S 6+ ‐9·43) r 2 = 0·987, where the glucosinolate content is expressed as μmol g −1 and the S 6+ content in mg g −1 . The relationship is applicable to seed of any glucosinolate content and to meal, and is unaffected by changes in protein sulphur content. The correlation of glucosinolates with S 6+ is shown to be closer than the correlation with total S. The latter correlation forms the basis of the existing XRS method, used within the European Community in recent years. The advantages of S 6+ derive from the linearity of the regression and the elimination of errors caused by variation in protein content. The method should be valuable to the Australian oilseed industry because it allows the rapid screening of breeding lines to ensure low glucosinolate content and the assessment of deliveries for crushing and of meal.