Poly‐p‐phenyleneterephthalamide (PPTA) is widely used in national defense, military industry, and aerospace. However, with weak compression resistance and twist resistance, development of PPTA is greatly impeded. In this work, a novel rigid rod polymer was synthesized by polycondensation of 2,6‐dihydroxyterephthalic acid with 2,3,5,6‐tetraminopyridine which have a large quantity of hydrogen bonds between these polymer chains which provide excellent thermal properties named poly [N‐(2,5‐diamino‐6‐[imino]‐3‐pyridyl)‐4‐formyl‐2,6‐dihydroxybenzamide] (PPDA). The structure of the polymers was characterized by X‐ray diffraction and Fourier transform infrared spectroscopy. The resulting showed that PPDA has good thermal stability and crystallinity, the maximum thermal decomposition temperature close to 900°C under the nitrogen atmosphere. At the same time, PPDA was insoluble in most organic solvents and exhibited good chemical stability. This indicated a superior performance over that of the poly(2,6‐diimidazo(4,5‐b:4′5′‐e)pyridinylene‐1,4(2,5‐dihydroxy)phenylene). In addition, we can foresee that PPDA will play an important role in prospective surgery and aramid areas.