Imidazole ring is an important five-membered aromatic heterocycle that is widely present in natural products and synthetic molecules. The isocyanide-isocyanide [3+2] cross-cycloaddition reaction constitutes a straightforward method to access imidazoles starting from the easily available chemicals. So far, only three successive reports are known and all lead to the formation of 1,4-disubstituted imidazoles. Here, we report the first isocyanide-isocyanide [3+2] cross-cycloaddition reaction allowing for the formation of 1,4,5-trisubstituted imidazoles under silver catalysis. An unexpected 1,2-migration of sulfonyl, alkoxycaybonyl, and carbamoyl groups took place during the cyclization process that is responsible for the formation of trisubstituted imidazoles. This report displayed a mechanistically novel synthetic method toward a variety of imidazole derivatives, which are otherwise difficult to access by conventional methods.