Synthesis and structural, photo physical, and conformational behaviors at variable temperature and structural optimization of the pyromelliticdiimide-based bromo-substituted [2 + 2] macrocycles are described. Cyclization of the diamine (3) with dianhydride (4) in THF, followed by dehydration of the resultant amic acids resulted in the isolation of the bromo-substituted [2 + 2] macrocycle 1 (4.5%). The dynamic temperature-dependent 1H NMR spectra and MO calculations revealed the presence of two possible conformers for the [2 + 2] macrocycle 1. The UV/Vis spectrum of 1 reveals the presence of a weak intramolecular CT interaction of electron-withdrawing pyromelliticdiimide moiety with the electron-donating hexyloxy-substituted xylyl moiety. The cyclic voltammetric measurement shows two two-electron reversible reduction processes.