A novel polyimide (PI)/clay hybrid nanocomposite, designated as PI (PAAS)/CM, has been developed from the poly(amic acid) salt of triethylamine and organomontmorillonite (CM) using a mixture solution of tetrahydrofuran (THF) and methanol (MeOH). For comparison, two other PI/clay hybrids derived from poly(amic acid) and CM in THF/MeOH solution and N,N'-dimethylacetamide (DMAc) solution, denoted as PI/CM (T/M) and PI/CM (DMAc), respectively, were also prepared. Dispersion of CM in polymer matrix, tensile properties, and thermal expansion properties of the three hybrids were investigated. Results show that PI (PAAS)/CM has the best dispersion of CM in polymer matrix, highest elongation, and lowest coefficient of thermal expansion values in all hybrids presented in this report. In addition, PI/CM (T/M) has better dispersion of CM and lower coefficient of thermal expansion value than PI/CM (DMAc).