The wettability of ionic liquids (ILs) is relevant to their use in various applications. However, a mechanistic understanding of how the cation-anion pair affects wettability is still evolving. Here, focusing on phosphonium ILs, wettability was characterized in terms of contact angle using experiments and classical molecular dynamics simulations. Both experiments and simulations showed that the contact angle was affected by the anion and increased as benzoate < salicylate < saccharinate. Further, the simulations showed that the contact angle decreased with increasing cation alkyl chain length for these anions paired with five different tetra-alkyl-phosphonium cations. The trends were explained in terms of adhesive and cohesive energies in the simulations and then correlated to the atomic scale differences between the anions and the cations.