AbstractThis paper reviews hydroxyl‐terminal polybutadiene (HTPB) used as liner and binder for composite propellants, applied in rocket motors studied throughout the last decades, emphasizing the recent advances. The contribution aims to show the importance of HTPB in the propellant composition and on the liner coating of the rocket motor, which is in contact with the propellant grain. This paper also shows that many researchers have thoroughly studied several properties of HTPB, which are relevant to its role in liners and propellants. We have also reviewed analytical techniques such as Fourier Transform Infrared Spectroscopy (FTIR) as a characterization technique for HTPB and HTPB‐based polyurethanes. Reflection and transfectants FTIR may be a future trend in studies about polymeric matrices for liners and propellants, and in the area of propellant formulations that use energetic binders, graphene and nanomaterials.