An alicyclic tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α´-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) was synthesized from a cyclopentanone bis-spironorbornene compound by Pd-catalyzed methoxycarbonylation, followed by the ester-exchange reaction and then by the thermal dehydration ring-closure. The dianhydride was polycondensated with 1,3-bis(4-aminophenoxy)benzene in DMAc to give a poly(amic acid) having an inherent viscosity ηinh of 0.31 dL/g. The viscous solution was cast on a glass plate. The plate was heated in vacuum at 80°C and 250°C for 1 h each to be converted to the polyimide film. The film was soluble in common organic solvents such as chloroform and possessed an averaged transmittance of 89.0% in the visible light area. The polyimide has good thermal stability with the 5% weight-loss temperature at 487°C and the Tg at 290°C. The high Tg may be due to a dipole-dipole interaction between the keto groups of the polymer chains as well as to a development of rigid polyalicyclic units.