Certain structurally modified polyisophthalamides with bulky azo pendent groups were prepared from the polycondensation of 5-(4’-dimethylaminoazobenzene) isophthaloyl chloride with various aromatic diamines. The corresponding unmodified polyisophthalamides were also synthesized to compare their properties. The modified polyisophthalamides showed higher solubility in certain solvents, such as 1,4-dioxane, m-cresol, cyclohexanone, and CCI3COOH, than the parent polyamides. The hydrophilicity of the modified polyisophthalamides was estimated by water absorption measurements, and it was found to be significantly higher than that of the corresponding unmodified counterparts. The modified polyisophthalamides were crosslinked upon heat curing, and they were stable up to 340-374 degrees C in N-2 or air and afforded anaerobic char yields of 68-72% at 800 degrees C.