The aroma compounds in broccoli stored in different modified atmospheres were studied. The packaging materials used were oriented polypropylene (OPP), poly(vinyl chloride) (PVC), and low-density polyethylene (LDPE) containing an ethylene-absorbing sachet. All samples were stored for either 1 week at a constant temperature of 10 °C or for 3 days at 4 °C, followed by 4 days at 10 °C. The atmospheres that developed inside the packaging materials differed significantly. The broccoli samples were analyzed raw and after cooking, with regard to volatile compounds, using gas-phase (headspace) extraction followed by gas chromatography-mass spectrometry (GC-MS) and GC-olfactometry. Dimethyl sulfide (DMS), dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS), hexanal, 3-cis-hexen-1-ol, nonanal, ethanol, and a group of thiocyanates were selected for a detailed study because these compounds cause off-odor and can be used as indicators of stress. Significant differences were found in the aroma profiles of the broccoli samples relative to the packaging materials used for storage. Storage in OPP (14% 02, 10.5% CO2) resulted in most of the off-odors, while storage in LDPE (6% 02, 7% CO 2) and PVC (17.9% 02, 4% CO2) was found to maintain the concentration of DMS, DMDS, and DMTS during storage. Heat treatment of the broccoli increased the content of aroma compounds as well as the number of compounds containing sulfur.