This work highlights the use of 3‐vinyl‐1,2,4‐triazines as original thia‐Michael acceptors and inverse electron demanding Diels‐Alder platforms en route to new 7,8‐dihydro‐5H‐thiopyrano[4,3‐b]pyridines. The required but rather unstable propargylthiol nucleophiles were successfully generated in‐situ upon an innovative DBU‐catalyzed methanolysis event of the corresponding propargyl thioacetate derivatives.magnified image