The crystallization process of the thermoplastic polyimide derived from 3,3’,4,4’-benzophenonetetracarboxylic dianhydride (BTDA) and 2,2-dimethyl-1,3,-(4-aminophenoxy) propane (DMDA) is studied at the molecular level by utilizing infrared spectroscopy’s sensitivity to local molecular environment. Assignments of the unique spectral features appearing upon crystallization are made with additional verification from crystalline model imide compounds. A direct comparison of an annealed polyimide film studied by both infrared spectroscopy and x-ray diffraction shows fairly close agreement in the amount of crystallinity obtained. The unique crystalline infrared spectral features provide insight into the molecular mechanism involved with the crystallization process. Spectral shifts occurring upon crystallization reflect intramolecular rotations toward increased coplanarity as well as intermolecular chain packing of certain molecular groups at specific sites of the chain backbone. The site specific information is then used to study the relative kinetic behavior of the intramolecular and intermolecular effects occurring during crystallization.