Supramolecular tessellation with self-synthesized (C₆₀)₇ tiles is achieved based on a cooperative interaction between co-adsorbed C₆₀ and octanethiol (OT) molecules. Tile synthesis and tiling take place simultaneously on a gold substrate leading to a two-dimensional lattice of (C₆₀)₇ tiles with OT as the binder molecule filling the gaps between the tiles. This supramolecular tessellation is featured with simultaneous on-site synthesis of tiles and self-organized tiling. In the absence of specific functional groups, the key to ordered tiling for the C₆₀/OT system is the collective van der Waals (vdW) interaction among a large number of molecules. This bicomponent system herein offers a way for the artificial synthesis of 2D complex vdW supramolecular tessellations.