Six-membered pincer nickelacycle complexes have been synthesized and employed for the catalytic C-H bond alkylation of benzothiazole. The pincer nickelacycle, {κ P , κ C , κ P-(2-i Pr 2 POCH 2-C 6 H 3-6-CH 2 OP i Pr 2)}NiBr, [(i Pr 4-POCCCOP)NiBr (2)] was synthesized by the reaction of 1,3-i Pr 2 POCH 2-C 6 H 4-CH 2 OP i Pr 2 [(i Pr 4-POCCCOP) − H (1)] with (CH 3 CN) 2 NiBr 2 in the presence of Et 3 N via the C(2)-H activation on ligand 1. Treatment of [(i Pr 4-POCCCOP)NiBr] (2) with AgOAc afforded the complex [(i Pr 4-POCCCOP)Ni(OAc)] (3) in good yield. Both the complexes 2 and 3 were characterized by 1 H, 13 C and 31 P-NMR spectral analysis. Further, the molecular structures of complexes 2 and 3 were established by X-ray crystallography. The complex 2 was found to be an active catalyst for the C-H bond alkylation of benzothiazole with alkyl halides containing β-hydrogen atoms.