Macrocycles denoted as saucer[n]arenes (n=4,5) were easily synthesized by the one-pot condensation of 2,7-dimethoxynaphthalene (2,7-DMN) and paraformaldehyde in the presence of TFA or catalytic BF 3 ⋅OEt 2 . With 1,1-dimethylpiperidin-1-ium as the template, saucer[4]arene was selectively obtained. Crystal structures show that saucer[n]arenes are all composed of 2,7-DMN moiety bridged by the methylene groups at 1,6-positions: all of the 7-methoxy groups lie on one face, and all of the 2-methoxy groups lie on the other. Saucer[n]arenes exhibit strong fluorescence properties with the quantum yields of 19.6 % and 23.4 %. They form 1:1 complexes with ammonium salts in both solution and solid state (association constant up to 10 5 M -1 in CDCl 3 ). Chiral quaternary ammonium salts can induce the chirality of the dynamically racemic inherently chiral saucer[n]arenes in solution, and thus show mirror-imaged circular dichroism signals and circularly polarized luminescence (CPL) properties., (© 2021 Wiley-VCH GmbH.)