Herein we report on the 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) catalyzed enolate‐mediated regiospecific synthesis of 1,4,5‐trisubstituted N‐vinyl‐1,2,3‐triazoles from simple activated carbonyl compounds and N‐vinyl azides through [3+2] cycloaddition; upon further hydrogenation, 1,4,5‐trisubstituted N‐alkyl‐1,2,3‐triazoles are furnished. Both the organo‐click and hydrogenation reactions proceeded in excellent yields with high rates and selectivities at 25 °C within a few hours.