Ionic liquids (ILs) have both fundamental and practical value in interfacial science and electrochemistry. However, understanding their behavior near a surface is challenging because of strong Coulomb interactions and large and irregular ionic sizes, which affect both their structure and energetics. To understand this problem, we present a combined experimental and computational study using a vibrational probe molecule, 4-mercaptobenzonitrile, inserted at the junction between a metal and a variety of ILs. The vibrational frequency of the nitrile in the probe molecule reports on the local solvation environment and the electrostatic field at this junction. Within the ethylmethyl imidazolium (EMIM+) cation family of ILs, we varied the anions over a range of sizes and types. Complementing our surface spectroscopy, we also ran molecular dynamics simulations of these interfaces to better understand the ionic structures that produced the measured fields. The magnitude of the frequency shifts, and thereby fields, shows a general correlation with the size of anions, with larger anions corresponding to smaller fields. We find that the source of this correlation is partial intercalation of smaller anions into the probe monolayer, resulting in tighter packing of ionic layers near the surface. Larger anions reduce the overall lateral ion packing density near the surface, which reduces the net charge per unit area and explains the smaller observed fields. The insight from this work is important for developing a fundamental picture of concentrated electrolytes near interfaces and can help with designing ILs to create tailored electric fields near an electrode.