SPME-GC-MS analysis on four samples of saffron from different areas of Italy and from Iran were performed. Sample 1 was derived from cultivations of Crocus sativus in the zone of Salerno (Southern Italy). Sample 2 was derived from cultivations in Sardinia, Italy. Sample 3 was derived from cultivations in Abruzzo (Central Italy). Sample 4 was derived from Iran. The main components were those found in ethereal extract of saffron in a work published in 1971. Several compounds found by using other extraction-distillation techniques were not found. We found 18 compounds never discovered in saffron. In all the samples, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,5,5-trimethyl-2-cyclohexen-1,4-dione, safranal and 2,4,4-trimethyl-6-hydroxy-3-carboxaldehyde-2,5-cyclohexadien-1-one were found. 3,5,5-Trimethyl-1,4-cyclohexandione was found in three samples. 5,5-Dimethyl-2-methylene-1-carboxaldehyde-3-cyclohexene, β-ionone were found in six samples, and nonanal, and 2,6-di-t-butylphenol were found in two samples. These compounds represent the compounds found with the highest frequency. Considering the relative amount of the components, safranal is the main component in all the samples. The analyses show that saffrons from different cultivation sites have some peculiarities due to the presence of some unusual components. The sample from Iran showed the presence of 3,5,5-trimethyl-2-hydroxy-2-cyclohexen-1-one, 2,7,7-trimethyl-2,4-cycloheptadien-1-one, 1,3,3-trimethyl-2-(E-2-butenylidene)-3-cyclo-hexene, 5,5-dimethyl-1,3-cyclohexadien-1-carbaldehyde, 1,1,3-trimethyl-2-(Z-2-butenylidene)-3-cyclohexene, 1-acetyl-5,5-dimethyl-bycyclo[3.1.0]hexane, and β-ionol.