Crithmum maritimum L., known as sea fennel, is an aromatic halophyte typical of the cliffs and coastal areas of the Mediterranean Sea and Atlantic Ocean. Their phytochemicals have been of great interest in the food and pharmaceutical industry. In this work, we analyzed, by SPME/gas chromatography coupled with mass spectrometry, the chemical variability of C. maritimum accessions in terms of volatile organic compounds. C. maritimum seeds were collected from different coastal sites in Salento, Southern Apulia, Italy, and subsequently cultivated ex situ. Several volatile compounds produced by C. maritimum leaves were detected, and, among them, D-limonene was found to be emitted at high levels by plants of all accessions representing the main compound, while other monoterpenes were produced at low levels. Moreover, the phenylpropene volatiles dillapiol and apiol (designated together as (dill)apiol) were emitted at variable amounts with different accessions. The correlation among groups based on volatile compounds has been analyzed using hierarchical cluster analysis, which has revealed three main groups based on (dill)apiol presence and its total amount in the cultivated plants of different geographic origins, confirming intraspecies biodiversity. Moreover, we have evaluated the seed germination and seedling development of C. maritimum in controlled conditions. We found no dormancy and a high germination rate for all samples analyzed. The chemo-diversity evidenced in cultivated plants obtained from seeds collected at different locations on the Salento peninsula is probably related to variations in climate resulting from different exposures along the coast. These findings highlighted the importance of C. maritimum as a suitable candidate for cultivation because it can tolerate harsh conditions/stresses and also has a possible use besides food and pharmaceuticals and for the restoration of coastal environments.