The adsorption of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on a rutile TiO(2)(011)-(2 × 1) surface is studied using ultra-high vacuum scanning tunneling microscopy. The self-assembly process is dominated by the fine interplay between the lateral intermolecular interactions and the binding to the substrate. By means of temperature-induced change in the adsorption configuration and the activation of diffusion, the molecules are assembled into one-dimensional chains oriented along the [Formula: see text] crystallographic direction.