Since their discovery, [2.2]paracyclophane (pCp) and its derivatives have fascinated the scientific community due to their original molecular architecture and unusual electronic behavior. Over the years, significant efforts have been devoted to the development of substituted pCps for a variety of applications in different fields, ranging from organic synthesis and asymmetric catalysis to polymer chemistry and material science. This review describes a series of useful approaches that allow chemists to selectively decorate pCps, control the planar chirality that these molecules can display as soon as they are functionalized, and tune their photophysical behaviors. For each of these aspects of paracyclophane chemistry, selected examples of major advances are presented, and possible directions for future research are outlined. The application of pCp as central core for the development of uncommon 3D luminophores is finally highlighted. Emphasis is placed on the potential use of planar chiral luminescent paracyclophanes as antennas or ligands for the design of multifunctional lanthanide complexes, a quite underdeveloped but highly promising area for future research endeavors.