jats:pWe review a number of recently developed strategies for enhanced sampling of complex systems based on knowledge of the potential energy landscape. We describe four approaches, replica exchange, Kirkwood sampling, superposition‐enhanced nested sampling, and basin sampling, and show how each of them can exploit information for low‐lying potential energy minima obtained using basin‐hopping global optimization. Characterizing these minima is generally much faster than equilibrium thermodynamic sampling, because large steps in configuration space between local minima can be used without concern for maintaining detailed balance. jats:italicWIREs Comput Mol Sci</jats:italic> 2015, 5:273–289. doi: 10.1002/wcms.1217</jats:p>jats:pThis article is categorized under: <jats:list list-type="explicit-label"> jats:list-itemjats:pStructure and Mechanism > Molecular Structures</jats:p></jats:list-item> jats:list-itemjats:pStructure and Mechanism > Computational Biochemistry and Biophysics</jats:p></jats:list-item> jats:list-itemjats:pStructure and Mechanism > Computational Materials Science</jats:p></jats:list-item> </jats:list></jats:p>