The crystallization of materials from a supersaturated solution is a fundamental chemical process. Although several very successful models that provide a qualitative understanding of the crystal growth process exist, in most cases the atomistic detail of crystal growth is not fully understood. In this work, molecular dynamics simulations of the morphologically most important surfaces of barite in contact with a supersaturated solution have been performed. The simulations show that an ordered and tightly bound layer of water molecules is present on the crystal surface. The approach of an ion to the surface requires desolvation of both the surface and the ion itself leading to an activated process that is rate limiting for two-dimensional nucleation to occur. However, desolvation on specific surfaces can be assisted by anions adsorbed on the crystal surface. This hypothesis, corroborated by crystallization and scanning electron microscopy studies, allows the rationalization of the morphology of barite crystals grown at different supersaturations.