This work included research of glucosinolate degradation products from six wild-growing Brassicaceae plants: Aurinia sinuata (L.) Griseb., Aurinia leucadea (Guss.) K. Koch, Bunias erucago (L.), Capsella rubella Reut., Cardaria draba (L.) Desv. and Sisymbrium officinale (L.) Scop. These plant species are widespread in the Mediterranean part of Croatia as well as in the area of the Marjan Forest Park (Split, Croatia). Degradation of glucosinolates was performed using the endogenous enzyme myrosinase. Isolation of glucosinolate degradation products (volatile compounds) was performed by headspace solid-phase microextraction method (HS-SPME), and the chemical composition and content of glucosinolate degradation products, as well as other volatile compounds, was performed by gas chromatography-mass spectrometry technique (GC-MS). Using indirect analysis method, namely HS-SPME/GC-MS, via isolation and identification of volatile hydrolytic products, glucosinolates from selected wild-growing Brassicaceae plants were identified. The main glucosinolates of Aurinia leucadea are gluconapin and glucobrassicanapin. The main glucosinolates of Aurinia sinuata are glucobrassicanapin and glucoberteroin. Number and content of glucosinolate degradation products in headspaces from Bunias erucago is rather small. However, according to HS-SPME/GC-MS analysis, it can be assumed that Bunias erucago contain four glucosinolates, glucodehidroerucin, gluconapin, glucoerucin and glucocaparin. The main constituents in headspaces from Capsella rubella are allyl-isothiocyanate and allyl-thiocyanate, so the main glucosinolate of Capsella rubella is sinigrin. Dominanting compound in headspaces from Cardaria draba is 4-(methylthio)butyl-isothiocyanate so it can be concluded that the main glucosinolate in Cardaria draba is glucoerucin. Considering that the most abundant compounds in headspaces of Sisymbrium officinale are isopropyl-isothiocyanate and sec-butyl-isothiocyanate, it can be concluded that the main glucosinolates from Sisymbrium officinale are glucoputranjivin and glucocohlearin.