The use of high-temperature nuclear magnetic resonance (NMR) spectroscopy provides a means of investigating the structure of refractory aluminate liquids at temperatures up to 2500 K. Time-averaged structural information indicates that the average aluminum coordination for magnesium aluminate (MgAl(2)O(4)) liquid is slightly greater than for calcium aluminate (CaAl(2)O(4)) liquid and that in both liquids it is close to four. Ion dynamics simulations for these liquids suggest the presence of four-, five-, and six-coordinated aluminate species, in agreement with NMR experiments on fast-quenched glasses. These species undergo rapid chemical exchange in the high-temperature liquids, which is evidenced by a single Lorentzian NMR line.