Syntheses of inwardly and outwardly directed allylsilanes those are tethered to new inherently chiral cavitands are described. Oxidized with mCPBA, these allylsilanes result in diastereomeric mixtures of epoxide molecules. Thus, it enables us to have comparative study of cavitand‐structure diastereoselectivity relationship, which revealed that an inward allylsilane group flanked by a dibenzo[f, h]quinoxaline and two bridged methylene groups have the best chemical yield and diastereoselection.