Two series of new aromatic polyimides were synthesized from 2,5-bis(4-aminophenyl)-1,3.4-oxadiazole and 2.5-diamino-pyridine and various diamidedianhydrides and dietherdianhydride via high-temperature poly-condensation in N-methyl-2-pyrrolidinone. The structures of polymers were characterized by means of FTIR, H-1 NMR spectroscopy, and elemental analysis; the results showed an agreement with the proposed structure. The polymers exhibited high glass-transition temperatures (T-g = 199-290 degrees C) and high thermal stability with decomposition temperatures (T-d) in the range of 437-510 degrees C. The optical properties, that is, absorption and photoluminescence (PL) of synthesized polymers, were investigated in solution and in solid state as a blend with inert poly(methyl methacrylate) (PMMA). The polymers in solution emitted violet-blue light in the range of 417-453 nm depending on the polymer structure. The polymers containing pyridine rings in the backbone emitted light at a longer wavelength than polymers with oxadiazole units. The effect of solvent polarity on polymer emission was found. Additionally, the photoluminescence properties of the polymers before and after protonation with HCl were tested.