Owing to their importance in natural product,biological and pharmaceutical chemistry,various methods have been developed for the synthesis of heteroaryl thioethers,which includes transition metal (TM)-catalyzed cross-coupling reactions with thiols,base-mediated nucleophilic aromatic substitution (SNAr) reactions with thiols,1 and SNAr reactions of heteroaryl halides with disulfides or phenylthiotrimethylsilane.2 However,these methods require toxic and smelly organosulfur reagents such as the thiols.We are also interested in using the readily available sulfur surrogates as the sulfur source in organic synthesis.3As our continuous interests in thioethers,2 utilization of sulfur surrogates in synthesis,3 and the use of alcohols as greener alkyl Sources,4 we now developed a new method for synthesis of unsymmetrical heteroaryl thioethers using thiourea as the sulfur surrogates and alcohols as the alkyl sources by a catalyst-,additive-,solvent-,and inert atmosphere-free direct MCR of heteroaryl halides.This new sulfur transfer method tolerates a wide range of substituted and functionalized substrates and can be extended to heteroaryl selenide synthesis.