After becoming associate professor, my investigations focused on polysaccharides properties. Particular emphasis was given to pioneering studies on the potentiality of synchrotron radiation x-rays spectroscopies for structural investigations and high resolution imaging of polysaccharidic systems. In the last 15 years, the structural studies of polysaccharides drove me to the investigation of the primary structure and conformational properties of polysaccharides produced by opportunistic. In this field, a large number of polysaccharides produced by strains of the Burkholderia cepacia complex, as well as other opportunistic bacteria, were structurally defined. Very recently, the scientific interest moved to the role of bacterial polysaccharides in biofilms. To this, bacterial polysaccharides were extracted directly from biofilms and structurally characterized. These investigation are among the first contribution on the accurate chemical characterization of polysaccharide composing biofilm matrices aiming at the clarification of the relationships between polysaccharide structure and biofilm properties.