Nanoscale structure-electric potential relations in films of the organic molecular semiconductors C(60) and titanyl phthalocyanine (TiOPc) on Ag(111) have been measured under UHV conditions. Noncontact force methods were utilized to image domain structures and boundaries with molecular resolution, while simultaneously quantifying the local surface electric potential. Sensitivity and spatial resolution for the local potential measurement were first established on Ag(111) through direct observation of the electrical dipole and potential step, φ(step) = 10 ± 3 mV, of monatomic crystallographic steps. A local surface potential increase of 27 ± 11 mV occurs upon crossing the boundary between the neat Ag(111) surface and C(60) islands. Potential steps in binary C(60)-TiOPc films, nanophase-separated into crystalline C(60) and TiOPc domains, were then mapped quantitatively. The 207 ± 66 mV potential step across the C(60)-to-TiOPc domain boundary exhibits a 3.6 nm width that reflects the spatial resolution for electric potential across a material interface. The absence of potential asymmetry across this lateral interface sets the upper bound for the C(60)-TiOPc interface dipole moment as 0.012 e nm.