In living systems, the adsorption of a protein on biointerfaces is a universal phenomenon, such as the specific binding of an antibody and antigen, which plays an important role in body growth and life maintenance. The exploration of a protein-selective adsorption on the biointerface is of great significance for understanding the life process and treatment in vitro. Herein, on the basis of biomimetic strategies, we fabricated a planar-chiral NH2-pillar[5]arene modified silicon surface (pR-/pS-NP5 surfaces) for a highly enantioselective adsorption of protein by taking advantage of the guest-induced planar chirality of pillar[5]arenes. Results from practical experiments and theoretical calculations show that the pR-NP5 surface possesses a high adsorption capacity and chiral selectivity for bovine serum albumin (BSA). Moreover, it was identified that the guest-induced chiral effect the generation and amplification of planar chirality, which was much beneficial for enhancing the interaction between planar-chiral pillar[5]arene host and BSA. The binding capacity of pR-NP5 and BSA is stronger than that of pS-NP5, thus promoting the chiral selective adsorption of BSA. This work affords a deeper understanding of the chiral influence of protein adsorption on biointerfaces and meanwhile provides a new perspective for chiral-sensing applications.