Adsorption and self-assembly of large π-conjugated 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on rutile TiO(2)(110) surface have been investigated using a combination of high-resolution scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations with inclusion of Grimme treatment of the dispersion forces (DFT-D). Evolution of the STM images as a function of PTCDA coverage is caused by transition of the adsorption mode from physisorbed single adspecies and meandering stripes into spontaneously ordered chemisorbed molecular assemblies. This change in the adsorption fashion is accompanied by significant bending of the intrinsically flat, yet elastic, PTCDA molecule, which allows for strong electronic coupling of the dye adspecies with the TiO(2) substrate. Extensive DFT-D modeling has revealed that adsorption is controlled by interfacial and intermolecular dispersion forces playing a dominant role in the adsorption of single PTCDA species, their self-organization into the meandering stripes, and at the monolayer coverage acting collectively to surmount the chemisorption energy barrier associated with the molecule bending. Analysis of the resulting density of states has revealed that alignment of the energy levels and strong electronic coupling at the PTCDA/TiO(2) interface are beneficial for dye sensitization purposes.