Chirality, as a fundamental symmetry property, plays an important role in molecular assembly in the solid state, impacting upon the properties and performance of organic materials. Here, heterochiral assembly was observed upon a binaphthol-based axially chiral material in the thin film state, where the heterochiral assemblies of racemic mixtures exhibit superior crystallization behavior and film morphologies than their homochiral counterparts. Additionally, a dramatic increase (nearly 2 orders of magnitudes) in electronic mobility was obtained upon switching the active layers of organic thin-film transistors from homochiral assemblies to heterochiral assemblies. This work not only gives insights into the structure-aggregation property relationships of axially chiral self-assemblies but also offers new opportunities for novel organic soft materials.