In recent years the importance of London dispersion forces as the attractive part of the van der Waals potential has been recognized for structural stability, catalysis and chemical reactivity. Though known for decades, the determination of the strength of dispersive interactions between certain groups remains a challenging task. Geometrically well‐defined molecular model systems offer the possibility to systematically examine and quantify the London dispersion contribution to interaction energies. The incorporation of control systems in the analysis allows dissecting the interaction of interest from other effects. The knowledge gained from these endeavours will provide the necessary basis to include London dispersion in the design of chemical processes and functional materials. Various molecular systems for the quantification of London dispersion of different groups have been reviewed. Each has its benefits and drawbacks. In general, the detailed knowledge of the contribution of London dispersion of specific groups will provide valuable guidelines for the design of molecular structures as well as processes.