Novel thermodynamically stable supramolecular donor-acceptor dyads have been synthesized. In particular, we assembled successfully C-60, as an electron acceptor, with the strong electron donor TTF through a complementary guanidinium-carboxylate ion pair. Two strong and well-oriented hydrogen bonds, in combination with ionic interactions, ensure the formation of stable donor-acceptor dyads. The molecular architecture has been fine-tuned by using chemical spacers of different lengths (i.e., phenyl versus biphenyl) and functional groups (i.e., ester versus amide), thus providing meaningful incentives to differentiate between through-bond and through-space electron-transfer scenarios. In electrochemical studies, both the donor and acceptor character of the TTF and C-60 units, respectively, have been clearly identified. Steady-state and time-resolved emission studies, however, show a solvent-dependent fluorescence quenching in C60(.)TTF dyads as well as the formation of the C-60(.-).TTF.+ radical ion pairs, for which we determined lifetimes that are in the range of hundred of nanoseconds to microseconds. The complex network that connects C60 with TTF in the dyads and the flexible nature of the spacer result in through-space electron-transfer processes. This first example of electron transfer in C-60-based dyads, connected by strong hydrogen bonds, demonstrates that this approach can add outstanding benefits to the construction of artificial photosynthetic systems that bear a closer resemblance to the natural one.