The molecular arrangement and chirality of the self-assembled arachidic anhydride monolayer on graphite were investigated using scanning tunneling microscopy (STM). This molecule has two identical alkyl chains, linked by an anhydride group in the middle. In its extended form, one alkyl chain is shifted, with respect to the other, along the molecular backbone. Upon adsorption on graphite, this achiral anhydride spontaneously forms two types of homogeneous domains (denoted as m and m') with mirror symmetry. The angle from the molecular chain to the row-packing direction is 98.0 degrees +/- 0.5 degrees and 82.0 degrees +/- 0.5 degrees for domains in and in', respectively. Domain m is the mirror image of m'. The molecular arrangement of this self-assembled monolayer shows that domains m and m' are two-dimensional enantiomers with opposite chiralities. This new molecular packing motif is confirmed by line-profile analyses along the molecule-chain and the row-packing directions. This finding demonstrates the spontaneous formation of highly ordered homogeneous enantiomorphous domains on graphite resulting only from weak van der Waals forces between the achiral arachidic anhydride molecules.