Broccoli is characterized by its specific flavor, which is the reason it is not tolerated by some consumers. The role of aroma in flavor is crucial; however, the characteristics of aroma-active components in broccoli are still unclear. Solvent-assisted flavor evaporation (SAFE) with the aid of solid-phase microextraction (SPME) and fractionation using solid phase extraction (SPE), followed by different chromatography-mass spectrometry approaches (GC-MS, GC-MS/MS, GCxGC-ToFMS) were used to identify the compounds of interest. A total of 33 aroma-active compounds were detected with the use of gas chromatography-olfactometry (GC-O) in raw, and 9 in cooked broccoli florets; in majority sulfur compounds-thiols, sulfides, and isothiocyanates prevailed. Methanethiol and 1-pentanethiol were the key odorants characterized by the highest FD (1024) in raw broccoli, followed by dimethyl sulfide, 2,3-butanedione, dimethyl trisulfide, dimethyl tetrasulfide, 2-methyl methanethiosulphonate, 4-methylpentyl isothiocyanate, hexyl isothiocyanate (all with an FD of 256). In cooked broccoli, the number and especially the intensity of detected compounds were much lower. The highest FD values (FD=4) were noted for dimethyl trisulfide and 1,4-octadien-3-one. To our knowledge, this is the first detailed identification of odorants in raw and cooked broccoli.