Enantioselective sensing and separation represent formidable challenges across a diverse range of scientific domains. The advent of hybrid chiral membranes offers a promising avenue to address these challenges, capitalizing on their unique characteristics, including their heterogeneous structure, porosity, and abundance of chiral surfaces. However, the prevailing fabrication methods typically involve the initial preparation of achiral porous membranes followed by subsequent modification with chiral molecules, limiting their synthesis flexibility and controllability. Moreover, existing chiral membranes struggle to achieve coupled-accelerated enantioseparation (CAE). Here, we report a replacement strategy to controllably produce mesoscale and chiral silica–carbon (MCSC) hybrid membranes that comprise chiral pores by interfacial superassembly on a macroporous alumina (AAO) membrane, in which both ion- and enantiomers can be effectively and selectively transported across the membrane. As a result, the heterostructured hybrid membrane (MCSC/AAO) exhibits enhanced selectivity for cations and enantiomers of amino acids, achieving CAE for amino acids with an isoelectric point (pI) exceeding 7. Interestingly, the MCSC/AAO system demonstrates enhanced pH-sensitive enantioseparation compared to chiral mesoporous silica/AAO (CMS/AAO) with significant improvements of 78.14, 65.37, and 14.29% in the separation efficiency, separation factor, and permeate flux, respectively. This work promises to advance the synthesis of two or more component-integrated chiral nanochannels with multifunctional properties and allows a better understanding of the origins of the homochiral hybrid membranes.