The development of heterogeneous, cost-effective and environmentally benign catalysts to construct CC bonds is highly desirable. We report here Co@N-doped carbon nanotubes (Co@NCNT) as a catalyst for a novel synthesis of styryl sulfides via dehydrogenative coupling of benzyl alcohols and DMSO under anaerobic conditions. This reaction maintains high atom efficiency as the CC bond is formed without the cracking of the C–S bond. We proposed that Co modified N-doped carbon sites are the active sites, different from traditionally believed metal centers for dehydrogenative C–C coupling. Moreover, the Co@NCNT catalyst could be easily separated and recycled for at least six runs. This work opens up a new application of metal–N–C catalysts in CC bond-forming reactions in synthetic chemistry.