We propose in this paper an original approach to study the structure of the molten LiF-ZrF4 system up to 50 mol % ZrF4, combining high-temperature nuclear magnetic resonance (NMR) and extended X-ray absorption fine structure (EXAFS) experiments with molecular dynamics (MD) calculations. Zr-91 high-temperature NMR experiments give an average coordination of 7 for the zirconium ion on all domains of composition. MD simulations, in agreement with EXAFS experiments at the K-edge of Zr, provide evidence for the coexistence of three different Zr-based complexes, [ZrF6](2-), [ZrF7](3-), and [ZrF8](4-), in the melt; the evolution of the concentration of these species upon addition of ZrF4 is quantified. Smooth variations are observed, apart from a given composition at 35 mol % ZrF4, for which an anomalous point is observed. Concerning the anion coordination, we observe a predominance of free fluorides at low concentrations in ZrF4, and an increase of the number of bridging fluoride ions between complexes with addition of ZrF4.