In this article we determine the temperature-dependent structure of the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)amide ionic liquid using a combination of X-ray scattering and molecular dynamics simulations. As in many other room-temperature ionic liquids three characteristic intermolecular peaks can be detected in the structure function S(q). A prepeak or first sharp diffraction peak is observed at about q = 0.42 Å−1. Long range anion-anion correlations are the most important contributors to this peak. In all systems we have studied to date, this prepeak is a signature of solvation asymmetry. The peak in S(q) near q = 0.75 Å−1 is the signature of ionic alternation and arises from the charge ordered separation of ions of the same charge. The most intense diffraction peak near q = 1.37 Å−1 arises from short-range separation between ions of opposite charge combined with a significant contribution from cationic carbon-carbon interactions, indicating that cationic hydrophobic tails have significant contacts.