Organic molecules are of great interest for gas sensing applications. However, achieving high-performance gas sensors with high sensitivity, fast response, low consumption, and workability in humid conditions is still challenging. Herein, we report the rational design and synthesis of an ion-in-conjugation polymer, PADC (poly-4,4′-azodianiline-croconamide), obtained by the condensation of croconic acid with 4−4′diaminoazobenzene for gas sensing under humid conditions. The as-fabricated PADCbased gas sensor exhibits ultrahigh sensitivity (802.7 ppm −1 at 1 ppm), subppb detection limit, and high selectivity under humid air with an 80% humidity effect at a temperature down to 350 K. PADC shows good planarity, excellent thermostability, and a narrow band gap of 1.2 eV because of azobenzene fragments spacing previously repulsed biphenyl rings. Compared to previous humidity immunity works, PADC-based sensors realized humidity immunity at a relatively lower temperature, resulting in lower energy consumption.