A visible light‐induced Co‐catalyzed highly regio‐ and stereoselective reductive coupling of vinyl azaarenes and alkynes has been developed. Notably, Hünig's base together with simple ethanol has been successfully applied as the hydrogen sources instead of commonly used Hantzsch esters in this catalytic photoredox reaction. This approach has considerable advantages for the straightforward synthesis of stereodefined multiple substituted alkenes bearing an azaarene motif, such as excellent regioselectivity (>20 : 1 for >30 examples) and stereoselectivity (>20 : 1 E/Z), broad substrate scope and good functional group compatibility under mild reaction conditions, which has been utilized in the concise synthesis of natural product monomorine I. A reasonable catalytic reaction pathway involving protolysis of the cobaltacyclopentene intermediate has been proposed based on the mechanistic studies. A novel regio‐ and stereoselective reductive coupling of vinyl azaarenes and alkynes has been developed to access functionalized azaarene compounds bearing stereodefined tri‐substituted alkenes via photoredox cobalt dual catalysis. Simple organic base together with alcohol has been applied as the hydrogen sources instead of commonly used Hantzsch esters in this coupling reaction.