A novel dianhydride containing nathphalene units was prepared by Ullmann reaction of 4-bromo-1,8-nathphalic anhydride with trimethylenedipiperidine and polymerized with various aromatic diamines in one-pot polycondensation at high temperature in m-cresol. All the polyimides are soluble in organic solvents and form transparent yellow thin films by solution casting. Their inherent viscosities were ranged in 0.17 - 0.68 dL/g (in m-cresol at 25square). The glass transition temperatures were from 202.7square to 263.6square by DSC. These polymers did not show appreciable decomposition up to 380square in N-2 by TGA and can emit strong green fluorescence in solution and in solid state. They may be potential light emitting and solar energy conversion materials.