The use of chiral ligands to tune the reactivity and enantioselectivity of transition‐metal catalyst for asymmetric transformations is a central challenge in synthetic organic chemistry. In this manuscript, chiral P‐ligand (Tao‐Phos)‐assisted Cu₂O‐nanoparticles‐catalyzed asymmetric azide–alkyne Huisgen cycloaddition is reported. The unique features of Tao‐Phos were determined in the copper‐catalyzed desymmetrization of pyrazolone‐derived bisalkynes through catalytic asymmetric Huisgen [3+2] cycloaddition (CAHC). This CAHC transformation resulted in good yields with moderate to high enantioselectivities.