By using a simple anthracene derivative with four alkoxy tails, a two-dimensional patterned surface was fabricated. The two-dimensional structures were directly visualized by scanning tunneling microscopy (STM) at the solid/liquid interface. The anthracene derivative formed highly ordered structures displaying cavities into which solvent molecules of 1-phenyloctane were coadsorbed. The functionality of the patterned surface was demonstrated by activating host-guest chemistry as the solvent molecules could be replaced by coronene, whose size is almost identical to the cavities formed by the anthracene derivative. Furthermore, [4 + 4] photodimerization of the anthracene derivative was performed at the solid/liquid interface and revealed that the physical height and electron density of the states were changed, resulting in the increase of an apparent height in the STM images. We demonstrate thus that the porous network of the two-dimensional pattern created by the anthracene derivative can be applied for selectively incorporating guest molecules and for photoprocessing.