[n]CycloParaPhenylenes (CPPs) molecules are synthesized by sequentially linking phenyl units in 1,4 position to form a macrocycle (see Fig. ). These non-planar cyclic π-conjugated systems have largely attracted the attention of theoretical and experimental groups, due to their unique electronic and optical properties and potential applications in Organic Electronics. In fact, these systems present variable emission spectra and quantum yields as a function of their size, in contrast with linear analogues. For instance, [10]CPP and some tetraalkoxy derivatives were used very recently to prepare thin-films in order to investigate their properties as electrontransport materials. In the field of supramolecular chemistry, [10]CPP is able to form a supramolecular concave-convex π-stacking complex with C 60 fullerenes in solution and solid-state, which can be further exploited to realize self-assembled functional materials.