The solid state structures of the carboxylic acid substituted pillar[5]arene PA5 host–guest complexes with ethanol and the anesthetic drug tetracaine are reported. PA5 forms an inclusion complex with ethanol in a 1 : 2 stoichiometry that assembles into hydrogen-bonded polymeric chains in the solid state. The macrocyclic cavity of PA5 can include large pharmaceutical molecules like tetracaine via a combination of different non-covalent interactions.