Acetonitrile is among the most commonly used nonaqueous solvents in catalysis and electrochemistry. We study its interfaces with multiple facets of the metals Ag, Cu, Pt, and Rh using density functional theory calculations; the structures reported shed new light on experimental observations and underscore the importance of solvent-solvent interactions at high coverage. We investigate the relationship of potential of zero charge (PZC) to metal work function, reporting results in agreement with experimental measurements. We develop a model to explain the effects of solvent chemisorption and orientation on the PZC to within a mean absolute deviation of 0.08-0.12 V for all facets studied. Our electrostatic field dependent phase diagram agrees with spectroscopic observations and sheds new light on electrostatic field effects. This work provides new insight into experimental observations on acetonitrile metal interfaces and provides guidance for future studies of acetonitrile and other nonaqueous solvent interfaces with transition metals.