A new diamine monomer, N,N'-bis(4-aminophenyl)-2,5-(diisopropoxycarbony)benzene-l,4-dicarboxamide was synthesized. Using the diamine, several alternating copolyimide precursors were successfully synthesized by its condensation polymerization with dianhydrides. The structure and properties (mechanical properties and thermal expansivity) of alternating copolyimides imidized thermally were characterized, and compared with those of the corresponding randomcopolyimides prepared from the copoly(amic acid)s. The alternating copolyimides exhibited relatively higher chain order and in-plane orientation in films than the random copolyimides. The higher chain order and in-plane orientation led to the higher tensile modulus and lower thermal expansivity in the alternating copolyimides. Such effect of comonomer sequence was found to be highly pronounced in copolyimides consisting of comonomers which have a large difference in the chain rigidity. It was demonstrated in this study that the formation of alternating copolyimides is a suitable route to improve the performance of properties.