Calix[5]arene-based artificial receptor 1 capped with chiral macrocycle 4 was synthesized and showed strong binding toward ethyltrimethylammonium salts via cation/pi and hydrogen-bonding interactions. The calix[5]arene cavity provided the dissymmetric guest-binding environment in which chiral guests 6-14 were encapsulated in an enantioselective fashion.