The energetics of multicomponent diffusion in molten CaO-Al2O3-SiO2 (CAS) were examined experimentally at 1440 to 1650°C and 0.5 to 2 GPa. Two melt compositions were investigated: a haplodacitic melt (25 wt.% CaO, 15% Al2O3, and 60% SiO2) and a haplobasaltic melt (35% CaO, 20% Al2O3, and 45% SiO2). Diffusion matrices were measured in a mass-fixed frame of reference with simple oxides as end-member components and Al2O3 as a dependent variable. Chemical diffusion in molten CAS shows clear evidence of diffusive coupling among the components. The diffusive flux of SiO2 is significantly enhanced whenever there is a large CaO gradient that is oriented in a direction opposite to the SiO2 gradient. This coupling effect is more pronounced in the haplodacitic melt and is likely to be significant in natural magmas of rhyolitic to andesitic compositions. The relative magnitude of coupled chemical diffusion is not very sensitive to changes in temperature and pressure.