Dictyotaceae, the large family of brown algae with the genus Dictyota as the richest one among them, produce a significant number of secondary metabolites, like diterpenes. The aim of this study was to investigate the variations in the composition of the volatile organic compounds (VOCs) of the brown alga Dictyota dichotoma collected from the Adriatic Sea. For the first time, both seasonal changes and the impact of air drying were examined. Headspace solid-phase microextraction (HS-SPME) on two fibres with different polarities and hydrodistillation (HD), followed by gas chromatography and mass spectrometry (GC-MS) analysis, was performed on both fresh (FrDd) and air-dried (DrDd) D. dichotoma. The major compounds of HS-FrDd were pentadecane and oct-1-en-3-ol. The percentage of pentadecane in HS-DrDd was increased up to 7.8 times in comparison with HS-FrDd. Principal component analysis (PCA) identified differences between the variability of data among fresh and dried samples over months and clearly dissociated the fresh May samples from the others in the HS-SPME results. The most abundant group of VOCs in HD were terpenes, with diterpenes isopachydictyol A and cembra-4,7,11,15-tetraen-3-ol as the major compounds. Diterpene pachydictyol A was also found and among sesquiterpenes and gleenol was the most abundant. Based on the dominant compound analyses, the PCA showed distinct separation of the fresh and dried samples, indicating similarities between the samples and allowing the establishment of typical VOCs significant for the chemotaxonomy of D. dichotoma.