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We report on the first measurements of the structure of compressed liquid boron, as it crosses the melt line in dynamic shock-compression experiments at a pressure of 100 GPa. Temporally, spectrally and angularly resolving x-ray scattering provides an independent and accurate measurement of the compression factor 1.5 and the electron density of 4 × 10 ^23  cm ^−3 at moderate temperatures of 0.2–1 eV. At these conditions, the elastic scattering measurements provide the structure factor and indicate the liquid compressed phase with a coordination number of 8.3 in good agreement with predictions from first-principles molecular dynamic simulations.