We have studied the role played by cyclic topology on charge-transfer properties of recently synthesized π -conjugated molecules, namely the set of [n]cycloparaphenylene compounds, with n the number of phenylene rings forming the curved nanoring. We estimate the charge-transfer rates for holes and electrons migration within the array of molecules in their crystalline state. The theoretical calculations suggest that increasing the size of the system would help to obtain higher hole and electron charge-transfer rates and that these materials might show an ambipolar behavior in real samples, independently of the different mode of packing followed by the [6]cycloparaphenylene and [12]cycloparaphenylene cases studied. ; This work is supported by the “Ministerio de Economía y Competitividad” of Spain and the “European Regional Development Fund” through Project CTQ2014-55073-P. M.M.M. thanks the E2TP-CYTEMA-SANTANDER program for financial support and the High Performance Computing Service of University Castilla-La Mancha for technical support.