In this study, a noncoplanar diimide diacid monomer (DIDA) was synthesized by direct condensation of trimellitic anhydride (TMA) with m-tolidine. The noncoplanar unit was incorporated into poly(amide-imide)s (PAIs) main chain by Yamazaki-Higashi phosphorylation of DIDA with various aromatic diamines. Encouragingly, all of the PAIs show good solubility in some common solvents such as N,N-Dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP), and m-cresol. In addition, the soluble PAIs show good optical transmittances of beyond 85 % at 500 nm due to the decreased crystallization ability. On the other hand, PAIs possess good mechanical properties with tensile strengths of 72–90 MPa and tensile moduli beyond 2 GPa. Meanwhile, the designed PAIs also exhibit excellent thermal properties: their glass transition temperatures ( T g ) range from 278 to 314 °C, initial decomposition temperatures (5 % weight loss temperatures, T 5wt% ) are beyond 470 °C, coefficients of thermal expansion (CTE) are below 10 ppm/°C. The excellent mechanical and thermal properties are due to the strengthened hydrogen bonding interaction among the amide groups. Therefore, it is believed that incorporating noncoplanar unit and amide group into the polymer main chain at the same time can simultaneously improve processability, optical transparency, mechanical and thermal properties. Furthermore, it is worth noting that the char of PAI at 800 °C is as high as 72.5 %, which is one of the highest known values. When PAI was incorporated into epoxy resin, the blend passed UL94 V-0 rating due to the high charring capability of PAI.