Five BINOL-based hosts with a variable macroring size were synthesized in a two-step postfunctionalization protocol by double N-benzylation followed by BMS-mediated reduction of tertiary amide groups (53−93%). UV−vis titration in MeCN reveals that all hosts exhibit a preference for the (R)-enantiomer over the (S)-enantiomer of PEA−HCl. The enantioselectivity depends on the number of hydrogen bond (HB) acceptors and the size and flexibility of the macroring. The highest enantiodiscrimination was observed for the 20-membered host 10, containing six HB acceptors (K R /K S = 2.13).