AbstractThe miscibility of chitosan and poly(vinyl pyrrolidone) −PVP‐ has been studied by viscosity measurements, differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). For chitosan/PVP blends in solid state (thin films) interaction were found by FTIR and DSC methods. After blending PVP with chitosan the glass transition temperature Tg was altered, this may be a result of hydrogen bonds between the synthetic and biological component. It was found that solution of chitosan and PVP are immiscible, viscosimetry methods showed that interactions between chitosan and PVP are to small for the predictions of miscibility, due to the high affinity of the two polymers for the solvent. The study of blends with bespoke structural and properties will be essential for the development of a new generation of biocompatible stimuli‐sensitive hydrogels.