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Physical and chemical properties of melts depend on the structural arrangements of atoms or building blocks, and their dynamics. Although intrinsically difficult to determine and to describe, the nature and the short-range to medium-range ordering of such units is the key to our understanding the systematics of melt properties, and for their extrapolation to inaccessible conditions of temperature, pressure, and composition. Vice versa, the variation of physical and chemical properties with composition may shed light on changes in structure. The structural approach to melt physics and chemistry is illustrated in the following for a variety of problems, from speciation of silicate polymeric units in model glasses and the structural role of aluminium in calcium aluminosilicate melts, to the effect of coordination of transition metals on the glass transition temperature and density, to influences of anionic species on viscosity, and finally to speciation and solubility of high-field-strength elements in melts.