Herein, we present a protocol starting from styrene oxide reacting with o‐acylaniline and o‐alkenylaniline derivatives to obtain 3,4‐disubstituted quinoline and 2‐acylquinoline derivatives, respectively, in 32‐92% yields under specific conditions. Preliminary research outcomes underscore the versatility of our approach, as exemplified by its scalability for large‐scale synthesis, downstream derivatization, and the characteristic properties manifested by the modified molecules.