Novel diamine monomers containing fluorine and phosphine oxide-bis(3-aminophenyl)-3,5-bis(trifluoromethyl)phenyl phosphine oxide (mDA6FPPO) and bis(3-aminophenyl)-4-(trifluoromethyl)phenyl phosphine oxide (mDAFPPO) - were utilized to prepare polyimides with dianhydrides such as 6FDA, BTDA or ODPA by the conventional two-step route, i.e. preparation of poly(amic acid) followed by solution imidization. The polyimides were characterized by FT-IR, NMR, DSC, and intrinsic viscosity measurements. The adhesion property of the polyimides was evaluated via a peel test with bare Cu foil, as well as silane/Cr-coated Cu foil, and failure surfaces were analyzed by SEM/EDX to elucidate the failure mechanism. The results were compared with those from the polyimides prepared from bis(3-aminophenyl)phenyl phosphine oxide (mDAPPO) containing only the phosphine oxide moiety, 1,1-bis(4-aminophenyl)-1-phenyl-2,2-trifluoroethane (3FDAm) containing only the fluorine moiety, and a commercial 3,3'-diaminodiphenylsulfone (mDDS). The polyimides with 3FDAm exhibited the highest T-g, followed by the mDAPPO-, mDA3FPPO-, and mDA6FPPO-based polyimides, but the mDAPPO-based polyimides exhibited the highest adhesion properties, followed by mDA3FPPO, mDA6FPPO, mDDS, and 3FDAm, which is attributed to the phosphine oxide and fluorine moieties.