Structure containing the CS bond exist widely in nature, drugs and chemical materials. Here, a novel sulfenylation protocol employing an aryl or alkyl halide and odorless and cheap S as reagents was developed, generating regioselective alkyl-S- and Ar-S-substituted imidazol[1,2-α]pyridine derivatives in good yields under relatively environmentally friendly and mild conditions. This protocol enriches current thioether-producing methods, making up for the shortcomings of previous sulfenylation methods which can only make MeS- and ArS-substituted imidazol[1,2-α]pyridine derivatives.