Nickel(0)-catalyzed [2+2+2] cycloaddition reaction of 1,6-diynes and nitrile has been limited to air and moisture sensitive Ni(COD)2 system. Here in, we studied air and moisture sensitive Ni(0) system through in situ generation of Ni-Xantphos species. Our system afforded the complementary regioisomers. The origin of the regioselectivity was explained by frontier molecular orbital interactions with DFT calculation.