Under catalyst-free conditions, an efficient method to synthesize 2-pyridinylamides has been developed, and the protocol uses inexpensive and readily available 2-fluoropyridine and amidine derivatives as the starting materials. Simultaneously, the copper-catalysed approach to imidazopyridine derivatives has been established with high chemoselectivity and regiospecificity. The results suggest that the nitrogen-heterocycles containing iodide substituents can also be compatible for the reaction via the cascade Ullmann-type coupling, and the nucleophilic substitution reaction provides the target products in a one-pot manner.