Great and continuous efforts have been made to discover high-performance engineering plastics with specific properties to replace traditional engineering materials in many fields. The utilization of machine learning (ML) has brought more opportunities for the discovery of high-performing engineering plastics. However, hindered by either the relatively small database or a lack of accurate structure descriptors with clear physical and chemical meanings relating to polymer properties, the current ML studies show some flaws in the accuracy and efficiency in polymer development. Herein, we collected a dataset of 878 polyimides (PI), one of the best engineering plastics, with experimentally measured glass-transition temperature (Tg) values, and developed a rapid and accurate ML approach to design PI candidates with the desired Tg value. After the conversion from PI structures into "mechanically identifiable" SMILES (Simplified molecular input line entry system) language, the eight most critical descriptors were ultimately obtained by multiple analysis methods. The physiochemical meaning of the key descriptors was further analyzed carefully to translate the implicit "machine language" to chemical knowledge. The artificial neural network (ANN)-based model gave the most accurate results with a root-mean-square error of ∼11 K among the studied ML methods. More importantly, three potential PI candidates with desired Tg (DPIs) were designed according to the chemical insight of the key descriptors, which were then verified by experiments. The experimental and predicted Tg values of DPIs have an acceptable average deviation of ca. 3.66%. This accuracy has reached the level of the traditional molecular simulation, but the time consumption and hold-up computing resource are tremendously reduced. Furthermore, the current ML approach could offer a scalable and adaptable framework in future engineer plastics innovation.