We study the physisorption of organic oligomers on the strongly ionic ZnO (10 1 0) surface by using first-principles density-functional theory and nonempirical embedding methods. It turns out that the in-plane variation of the molecule-substrate interaction energy and the bonding dipole in the vertical direction are linked up by a linear relationship originating from the electrostatic coupling of the molecule with the periodic dipolar electric field generated by the Zn-O surface dimers. Long oligomers with a highly axial π-electron system such as sexiphenyl become well oriented with alignment energies of several 100 meV along rows of a positive electric field, in full agreement with recent experiments. These findings define a new route towards the realization of highly ordered self-assembled arrays of oligomers or polymers on ZnO (10 1 0) and similar surfaces.