A tunable reaction manifold of alkynyl sulfonium salts with binucleophilic N-aryl amidines in the absence of any transition metal catalyst is first reported. This methodology involves sequential addition/cyclization that is perfectly tuned by stepwise addition of K2CO3, affording a plethora of valuable 1,2,4- and 1,2,5-trisubstituted imidazoles in good yields with high regioselectivity. Importantly, trapping and isolation of the reactive intermediate unveiled the reaction mechanism of β-attack on the triple bond in this [3 + 2] cycloaddition reaction.