The synthesis and characterization of Nickel(II) complexes with novel pincer‐type N‐heterocyclic carbene complexes were investigated. Nickel(II)‐NHC complexes, 7 and 8, were characterized using HR ESI‐MS, IR, UV‐Visible, and elemental analysis. The complex 7 with less sterically demanding pincer ligand was investigated in the catalytic one pot synthesis of thioethers via coupling reactions of a series of aryl and alkyl halides in the presence of thiourea. In a mixture of water and ethanol, 5 mol% of 7 catalyzed the C‐S bond coupling reaction in high yields.