The mixed ligand system 10 mol % NiCl(2)(dppp) with 5 mol % dppf was discovered to be an extremely efficient catalyst for the neopentylglycolborylation of a diversity of electron-rich and electron-deficient aryl chlorides. Optimization showed that 5 mol % catalyst with 10% dppf was even more efficient. These results highlight the complexity of the relationship between catalyst and coligand in Ni catalysis and the benefit of combinations of mixed ligand in catalyst design.