Despite macrocyclic arene chemistry has achieved rapid development in recent years, the synthesis of new macrocyclic arenes from the aromatic rings with no directing groups remains a considerable challenge. In this work, a new type of macrocyclic arene, naphth4arene (NA4A), composed of four naphthalene rings bridged by methylene groups, was successfully synthesized by a macrocycle-to-macrocycle conversion strategy. NA4A shows 1,3-alternate and 1,2-alternate conformations in solid state, and they can be selectively obtained. By supramolecular co-assembly of NA4A and 1,2,4,5-tetracyanobenzene (TCNB) in different concentrations and ambient temperatures, two conformation-dependent crystalline luminescent co-assemblies 1,2-NTC and 1,3-NTC can be selectively prepared as well. Interestingly, the two charge transfer crystalline assemblies containing NA4A with different conformation emit bright yellow and green fluorescence, respectively, and also display high photoluminescence quantum yields (PLQYs) of 45% and 43%. Furthermore, the two crystalline assemblies can exhibit color-tunable two-photon excited upconversion emission property. This work provides a new perspective and route for fabricating color-tunable supramolecular crystalline luminescent materials regulated by the conformations of macrocyclic arene.