Five fluorenyl cardo diamines containing different alkyl substituents were synthesized and characterized. A series of fluorenyl cardo polyimides were prepared by polycondensation of these cardo diamines with 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-biphenyl tetracarboylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA). Most of fluorenyl cardo polyimides exhibited excellent solubility in common organic solvents such as m-cresol, chloroform, tetrahydrofuran (THF), N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAC) etc. and intrinsic viscosity in N,N-dimethylacetamide (DMAC) ranged from 0.31 to 0.92 dl/g. T-g of polyimides based on ODPA decrease with the number and size of alkyl substituents on fluorenyl cardo diamine. The results show that the incorporation of noncoplanar structure led by the introducing alkyl substituents on fluorenyl cardo diamines improves the solubility of cardo polyimides in organic solvents without sacrificing thermal properties. (c) 2005 Elsevier Ltd. All rights reserved.