The invention discloses macrocyclic and cage-like molecules based on biphenylarene and derivatives of the macrocyclic and cage-like molecules as well as synthetic methods and applications of the macrocyclic and cage-like molecules and the derivatives. A series of novel macrocycles are obtained mainly by performing a reaction on bis(2,4-dialkoxyphenyl)arenes (naphthalene, anthracene, pyrene, porphyrin and the like) or tris(2,4-dialkoxyphenyl)arenes (benzene, sym-tribenzobenzene) and paraformaldehyde under the catalysis of a Lewis acid in high yield. In addition, perhydroxybiphenylarenes (quaterphenyl trimer, naphthalene dimer and the like) can be obtained by performing demethylation, a plurality of water-soluble derivatives can be obtained by performing further modification, and the derivatives show good bonding ability to guest molecules (viologen and the like); and moreover, functional groups introduced into the framework make the biphenylarene have excellent adsorption and separationability and photophysical properties. The compounds, derivatives and methods provided by the invention have the following advantages: raw materials of the biphenylarene are commercially available, the synthesis is simple and convenient, the yield is high, and the modification is convenient, so that the compounds and the derivatives have broad application prospects in gas adsorption and separation, performance improvement of light-emitting materials, and adsorption of water-soluble toxic substances.