Crystallization from solution is a crucial process used in the manufacture of a wide variety of materials. The first step in the crystallization process is the birth of a new crystalline phase, which is known as nucleation. Nucleation plays a key role in determining the results of any crystallization process with respect to the size, shape and crystal form obtained. Classical nucleation theory does not adequately explain the crystal nucleation process. Work described in the literature and at this Faraday Discussion describe more complex nucleation mechanisms which are generally known as two-step nucleation models. In addition, as most nucleation is influenced by dust, dirt and container surfaces, the importance of heterogeneous nucleation and the use of templates to accelerate nucleation and influence crystal form are promising methods for the study and control of nucleation. It is also clear from this Faraday Discussion that interest in this topic has grown, and new and novel experimental and modeling approaches are being used for the study of crystal nucleation from solution.