This study focused on bioglea in thermal material sampled at Saturnia spa (Tuscany, Italy). Bioglea is the term used to define the thermal plankton consisting of biogenic substances that have been investigated little from the chemical and biological points of view. Bioglea is mainly formed of cyanobacteria, particularly from the Oscillatoriales subsection, and it seems to have an important role in the maturation of thermal mud for the development of organic matter. This cyanobacteria-dominated community develops in a large outdoor pool at the spa, where the spring water is collected, over the sediments, with matter floating at the surface. Throughout the year, the cyanobacterial species of bioglea were the same, but their relative abundance changed significantly. For chemical characterization an extractive method and several analytical techniques (HPLC, GC-MS, SPME) were used. We also studied the radical scavenging activity using in vitro tests (DPPH, ORAC, ABTS). We found various groups of compounds: saturated and unsaturated fatty acids, hydroxyl acids, alcohols, phenols, amino acids. Many of the compounds have already been identified in the mud, particularly the lipid component. SPME indicated several hydrocarbons (C11–C17) and long-chain alcohols (C12–C16). The qualitative composition of volatile substances identified in bioglea was very similar to that of the mud previously analysed. These results contribute to our knowledge on thermal photosynthetic community and its possible exploitation.