Noncontact chemically resolved electrical measurements are presented, capable of probing selected regions within fine heterostructures. Using a slightly modified x-ray photoelectron spectrometer, an effective means is demonstrated for measuring I-V curves of molecular layers, free of substrate and contact contributions. The concept is simple and general, revealing unique details on electrical response mechanisms. Realized with commonly available equipment, it should be effective for a broad range of heterostructured systems. (C) 2004 American Institute of Physics.