A novel rigid-rod type dianhydride monomer with phosphine oxide moiety, 4-(diphenyl phosphine oxide)phenyl pyrromellitic dianhydride (POPPMDA), was synthesized via the Suzuki coupling reaction of 4-(diphenyl phosphine oxide)phenyl boronic acid (POBB) and 1-bromo-2,3,5,6-tetramethyl benzene (B4MB), followed by oxidation and cyclodehydration. The monomer was characterized by FTIR, NMR, EA, and melting point analyzer and utilized to synthesize polyimides with diamines such as bis(3-aminophenyl)phenyl phosphine oxide (mDAPPO) and p-phenylene diamine (pPDA) by varying their ratio. The polyimides were prepared via a conventional two-step synthesis: preparation of poly(amic-acid), followed by solution imidization. The polyimides were characterized by FTIR, NMR, DSC, TGA, and TMA, and their solubility, intrinsic viscosity, and adhesive properties were also evaluated. The polyimides exhibited high T g (342-362 C), good thermal stability (>500 C), excellent adhesive property (134-107 g/mm), and low CTE (28-17 ppm/ C).