We present the characterization of commercially available Poly(hexamethylene biguanide) hydrochloride (PHMB), a polymer with biocidal activity and several interesting properties that make this material suitable as a building block for supramolecular chemistry and “smart” materials. We studied polymer structure in water solution by dynamic light scattering, surface tension and capacitance spectroscopy. It shows typical surfactant behavior due to amphiphilic structure and low molecular weight. Spectroscopic (UV/Vis, FT-NIR) and thermal characterization (differential scanning calorimetry, DSC, and thermogravimetric analysis, TGA) were performed to give additional insight into the material structure in solution and solid state. These results can be the foundation for more detailed investigations on usefulness of PHMB in new complex materials and devices.