LiF–NaF–ZrF₄ multicomponent molten salts are identified as promising candidates for coolant salts in molten salt reactors and advanced high-temperature reactors. This study focused on low-melting point salt compositions of interest: 38LiF–51NaF–11ZrF₄, 42LiF–29NaF–29ZrF₄, and 26LiF–37NaF–37ZrF₄. Ab-initio molecular dynamics (AIMD) calculations were performed and compared with available experimental data to assess the ability of rigid ion models (RIM) to reproduce short- to intermediate-range structure, transport, and thermophysical properties of the LiF–NaF–ZrF₄ salt mixtures. It is found that as ZrF₄ mol% increases, the average cation–anion coordination number (CN) of monovalent cations (Li⁺, Na⁺) obtained from RIM calculations decreases, while multivalent Zr⁴⁺ CN varied from 15% to 19% in comparison to corresponding AIMD values. In addition, RIM is found to predict the existence of 7, 8, and 9 coordinated fluorozirconate complexes, while AIMD and the available experimental data showed an occurrence of 6, 7, and 8 coordinated complexes in the melt. The intermediate-range structure analysis revealed that while the RIM parameters are able to reproduce a local structure for lower ZrF₄ mol% salts such as in 38LiF–51NaF–11ZrF₄, an extensive fluorozirconate network formation is observed in RIM simulations for higher ZrF₄ mol% compositions. The network generated by RIM parameters is found to be mainly connected by “corner-sharing” fluorozirconate complexes as opposed to both “edge-sharing” and “corner-sharing” connectively portrayed by AIMD. It is found that a close agreement between AIMD and the RIM salt structure for the 11-mol% ZrF₄ salt resulted in good agreement in the calculated Zr diffusivities and the viscosity values. However, due to the inaccurate short- to intermediate-range structure prediction by RIM for higher ZrF₄ mol% compositions, thermophysical properties such as densities and heat capacity differ by up to 26% and 27%, respectively, upon comparison with AIMD and experimental values. Also, the network-dominated properties such as diffusion coefficients and viscosities differed by up to two and three orders of magnitude, respectively. This study signifies the importance of accurate salt structure generation for an accurate prediction of transport and thermophysical properties of multicomponent molten salts.