Organic-metal interfaces are key elements in organic-based electronics. The energy-level alignment between the metal Fermi level and the molecular orbital levels determines the injection barriers for the charge carriers at the interfaces, which are crucial for the performance of organic electronic devices. Dipole formation at the interfaces has been regarded as the main factor that affects the energy-level alignment. Several models have been proposed for the mechanism of dipole formation in the context of the interface between organic molecules and a bulk metal crystal surface, at which surface states were mostly used to probe the interfacial properties. Here we report that when the bulk metal crystal is replaced by a uniform metal thin film, the resulting two-dimensional quantum-well states will be able to not only probe but also modify the interfacial electronic structures, such as gap states, that have no counterpart at the organic-bulk crystal interface.