The growth of zigzag single-walled carbon nanotubes (SWNTs) is most challenging among all types of SWNTs, with the highest reported selectivity of ∼7%. Here we realized the dominant growth of (16,0) tubes at the abundance near ∼80% by using intermetallic W6Co7 catalysts containing plenty of (1 1 6) planes together with optimizing the growth conditions. These (1 1 6) planes may act as the structure templates for (16,0) SWNTs due to the geometrical match between the open end of the (16,0) tube and the atomic arrangements of the (1 1 6) planes in W6Co7. Using catalysts with designed structure as solid state template at suitable kinetic conditions offers a strategy for selective growth of zigzag SWNTs.