A series of easily prepared nicotine-derived ammonium salts were applied for the first time as recyclable and efficient catalysts for the coupling of carbon dioxide and epoxides to form cyclic carbonates at low pressure without using additional organic solvents and co-catalysts. Remarkably, excellent yields and selectivity were achieved when 1-benzyl-1-methyl-2-pyridin-3-yl-pyrrolidinium bromide [MBNT]Br was used as the catalyst. Furthermore, the catalyst can be easily recovered and reused without a significant loss of activity. The influences of the catalyst structure and various reaction parameters on the catalytic activity were also investigated in detail.