Given the comparatively lower rotational barriers, the catalytic asymmetric construction of axially chiral biaryl structures, especially those containing a five‐membered heterocycle, still remains a challenge. Herein, we described a general and modular protocol to access atropisomeric arylpyrazole scaffolds containing a phosphorus unit by a dipeptide phosphonium salt catalyzed reaction involving an oxidative central‐to‐axial chirality conversion. This reaction features excellent yields and enantioselectivities, broad substrate scope, and a low catalyst loading, delivering axially chiral phosphine compounds. A highly enantioselective reaction has been developed for the construction of axially chiral arylpyrazole skeletons with phosphorus unit. The reaction proceeds through a sequential Huisgen‐type cycloaddition/aromatization process with central‐to‐axial chirality conversion using a dipeptide‐phosphonium salt catalyst. Arylpyrazole‐based atropisomeric phosphorus compounds are obtained in high yields with excellent enantioselectivities.