The relationship between the molecular structure of polymeric binders and mechanical properties of a TATB‐based polymer bonded explosive (PBX) were studied by using five different fluoropolymers as binders to compare the quati‐stastic and dynamic mechanical property, as well as the three‐point bending creep property of the PBX. F‐ binder A, which was composed of vinylidene fluoride (VDF) and chlorotrifluoroethylene (CTFE), endowed the PBX−A with the best mechanical strength and creep resistance ability. The fracture surfaces of the PBXs after the Brazilian tests were investigated by a field emission‐scanning electron microscope (FE‐SEM). The rupture mode in PBX−A and PBX−B was transcrystalline fracture together with interfacial debonding, but only interfacial debonding in PBX−C and PBX−D. It was explained that the C−Cl bond in CTFE played the key role to keep the polymeric binder rigid and increase the strength of the PBX.