Rongalite has been used as a cheap and efficient carbon synthon for the synthesis of divergent N-heteroaromatics, including different pyridines and quinolines. The selective synthesis of different products can be achieved by employing enaminones or enaminones/anilines as reaction partners. In addition, compared with the reaction using conventional aldehyde synthons, rongalite displays an evident advantage in providing products with considerably higher product yields under milder conditions. The GC-MS analysis of the reaction process has been performed to probe the possible reaction mechanism.