Nicotine-based ionic liquid has been used as a green catalyst for pyridine-catalyzed Huisgen reaction. It promoted addition of dimethylacetylenedicarboxylate to aldehydes or N-tosyl imines leading to efficient synthesis of 2-benzoylfumarates and 1-azadienes respectively under pyridine free odorless ionic liquid conditions. The improved results were obtained in terms of enhanced yields, with minimal work up.