A convenient, efficient synthesis of 1, 2, 4-triazolines from α-isocyano esters/amides and azodicarboxylates is presented. The developed reaction cascade is based on a base- catalyzed hydrazination-type reaction followed by a subsequent cyclization providing the triazolines in good to excellent yields (75− 99%). Phosphine-catalyzed and preliminary asymmetric phase-transfer catalysis approaches have also been investigated.