Herein, we have developed a simple and efficient synthesis of α,β-alkynyl/alkenyl ketone derivatives by acid-catalyzed reactions of 2,6-dimethyl-N-(4-methylbenzylidene)aniline and alkynes. This methodology provides a novel pathway for the synthesis of α,β-alkynyl/alkenyl ketones via acid-catalyzed coupling reactions and subsequent silica gel catalyzed hydrolysis. Characterized by wide substrate scope, mild reaction conditions, and good to excellent yields this protocol may aid the further development of the C-C coupling reactions.