A series of aromatic diacylhydrazides containing pendent flexible alkoxy chains, viz., 5-butyloxyisophthalicacid dihydrazide, 5-octyloxyisophthalicacid dihydrazide, 5-dodecyloxyisophthalicacid dihydrazide and 5-hexadecyloxyisophthalicacid dihydrazide were synthesized by the hydrazinolysis reaction of the corresponding aromatic esters with hydrazine hydrate. Diacylhydrazides were each polycondensed with aromatic dianhydrides, viz., 4,4′-oxydiphthalic anhydride (ODPA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) to obtain new poly(amideimide)s. Poly(amideimide)s had inherent viscosity in the range 0.55–0.88 dL/g in N, N-dimethylacetamide (DMAc) at 30 ± 0.1 °C. Poly(amideimide)s were found to be soluble in DMAc, N, N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP) and pyridine and could be cast into tough, flexible and transparent films from a solution in DMAc. X-ray diffractograms revealed that poly(amideimide)s with longer alkoxy chains had layered structures. Glass transition temperature of poly(amideimide)s containing pendent flexible alkoxy chains were in the range 215–245 °C. Temperature at 10% weight loss was in the range 380–410 °C in nitrogen atmosphere indicating good thermal stability of poly(amideimide)s.