A new class of [2]catenanes containing zinc(II)-porphyrin (ZnP) and/or [60]fullerene (C60) as appended groups has been prepared. A complete description of the convergent synthetic approach based on Cu(I) template methodology and “click” 1,3-dipolar cycloaddition chemistry is described. This new electron donor-acceptor catenane family has been subjected to extensive spectroscopic, computational, electrochemical and photophysical studies. 1H NMR spectroscopy and computational analysis have revealed that the ZnP-C60-[2]catenane adopts an extended conformation with the chromophores as far as possible from each other. A detailed photophysical investigation has revealed that upon irradiation, the ZnP singlet excited state initially transfers energy to the (phenanthroline)2-Cu(I) complex core, producing a metal-to-ligand charge transfer (MLCT) excited state, which in turn transfers an electron to the C60 group, generating the ZnP–[Cu(phen)2]2+–C60·− charge separated state. A further charge shift from the [Cu(phen)2]2+ complex to the ZnP subunit, competitive with decay to the ground state, leads to the isoenergetic long distance ZnP·+–[Cu(phen)2]+–C60·− charge separated radical pair state, which slowly decays back to the ground state on the microsecond time scale. The slow rate of back electron transfer indicates that in this interlocked system, as in previously studied covalently linked ZnP-C60 hybrid materials, this process occurs in the Marcus inverted region.