Water is a demanding partner. It strongly attracts ions, yet some halide anions—chloride, bromide, and iodide—are expelled to the air/water interface. This has important implications for chemistry in the atmosphere, including the ozone cycle. We present a quantitative analysis of the energetics of ion solvation based on molecular simulations of all stable alkali and halide ions in water droplets. The potentials of mean force for Cl$^-$, Br$^-$, and I$^-$ have shallow minima near the surface. We demonstrate that these minima derive from more favorable water–water interaction energy when the ions are partially desolvated. Alkali cations are on the inside because of the favorable ion–water energy, whereas F$^-$ is driven inside by entropy. Models attempting to explain the surface preference based on one or more ion properties such as polarizability or size are shown to lead to qualitative and quantitative errors, prompting a paradigm shift in chemistry away from such simplifications.