Charge transport at or across molecule-electrode interfaces is central to the operation of a wide variety of molecule-based electroic devices. The critical charge transporting interfaces in most systems are buried interfaces which are not readily accessible to conventional structural or spectroscopic probes. For any given device, two critical questions are: (1) What is the structural and chemical nature of the molecules at the buried interface before or during operation? (2) How is the electrical conductance across an interface related to physical properties such as electronic energy level alignment and charge redistribution? This talk will attempt to address both questions from spectroscopic measurements and to demonstrate that such a spectroscopic view is of critical importance in achieving a quantitative understanding of moleular electronics.