Thermophilic microorganisms (4001-4014), described as aerobic or facultatively anaerobic, endospore forming with growth optima temperatures in the range of 60 to 80 degrees C, have been isolated from hot marine springs around Ischia and from hydrothermal vents in the gulf of Naples. Mucous colonies are been selected for the recovery of new strains producing exopolysaccharides (EPS). To induce the biosynthesis of new exopolysaccharides, different sugars were tested as carbon sources in the media. The production of EPS in the strain 4009 reached 60 mg/l using trehalose as carbon source, increasing the yield of about 1000 fold. The 4001-EPS was a mannan with a molecular weight of 380.000 D and with a complex primary structure. In fact, the analysis of the permethylated polysaccharide in GC-MS, showed the presence of mannose, glucose, galactose, mannosamine in the relative ratio of 1:0.1:tr :tr, respectively. Nuclear magnetic resonance spectrum of the exopolysaccharide confirmed the presence of a repetitive unity formed by seven monosaccharides, six with alpha gluco/galacto configuration and one residue with beta conformation.