A new monomer, 1,5-bis(p-dimethylaminophenylimino)naphthalene, was prepared through Schiff-base condensation reaction of 1,5-diaminonaphthalene and 4-(dimethylamino)benzaldehyde in the presence of ethanol. A series of aromatic polyimides bearing naphthalene and -CH=N-groups were synthesized from the diamine with five kinds of commercial dianhydrides via a conventional one-stage process. The resulting naphthalene based polyimides (NBPs) showed good solubilities in N-methyl-2-pyrrolidone and m-cresol. NBPs had glass-transition temperatures at 139-174 degrees C and 10% weightloss temperatures above 430 degrees C in nitrogen atmospheres. Excellent properties of NBPs are attributed to the incorporation of the naphthalene and -CH=N- group in 1,5-bis(p-dimethylaminophenylimino)naphthalene. Moreover, chemically prepared polyimides were used for immobilization of glucose oxidase (GOx). The amperometric responses of the NBPs-GOx-Pt electrodes toward glucose were examined at a potential of 0.7 V in PBS solution by means of time-base (TB) technique. Results show that NBPs bearing -O- group membrane (PI-3) has many advantages in the immobilization of glucose oxidase because of its strong adherence to electrode surface and chemical stability and selectivity. Copyright (C) 2010 John Wiley & Sons, Ltd.