A variety of novel chiral phosphoric acid catalysts were synthesized from R⁃binaphthol via hydroxyl protection, halogenation, coupling, deprotection, phosphorylation and hydrolysis. The chiral phosphoric acid catalysts synthesized were mainly chiral phosphoric acid catalysts with nitro substituents, because the addition of nitro substituents could increase the acidity of phosphoric acid and provide a catalyst for some reactions requiring a stronger acidic catalytic system. By our method, about 10 g of nitro⁃substituted chiral phosphoric acid catalyst could be synthesized in one time in a high yield, which provided great convenience for asymmetric catalytic reaction.