The self-assembly of the star-shaped 1,3,5-tris(4-iodophenyl)benzene molecule is investigated using scanning tunneling microscopy (STM) at the solid–liquid interface. This molecule forms dimers that self-assemble into two-dimensional porous halogen–halogen bonded nanoarchitectures on the graphite surface. STM shows that the structure of the porous organic network can be tailored using different solvents. Neighboring dimers are binded to each other through two iodine···iodine bonds in 1-phenyloctane, whereas 1-octanol solvent leads to the formation of I4 synthons connecting together four molecular dimers. Iodine bonds appear to be a promising alternative to hydrogen bonds to engineer new organic porous structures on surfaces.