The precise localization of organic molecules in controllable positions is an important step towards constructing functional nanostructures via the bottom-up strategy. Herein, supramolecularly organized C70-fullerene assemblies on macrocycle-modified surfaces were investigated using scanning tunneling microscopy (STM) in combination with theoretical calculations. The results revealed that an up-assembly of C70-fullerene adlayers was successfully formed on top of the bottom macrocycle arrays. Density functional theory (DFT) calculations confirmed that the macrocycle networks along with the co-adsorbed solvent 1-phenyloctane served as a selective template for trapping C70-fullerene molecules in the spectral sites and acted as a support for the C70-fullerene molecules. The periodical distribution of the C70-fullerene molecules should facilitate understanding of the strong dependence of the arrangement of C70-fullerene upon the specific interactions (apart from spatial recognition) derived from modification of the sub-monolayers.