Understanding the Liquid-Liquid Equilibrium (LLE) of multicomponent solvent/bitumen systems is pivotal in optimizing in-situ bitumen extraction. While Vapor-Liquid Equilibria (VLE) of solvent-bitumen systems has been extensively studied, LLE data and predictive models for these mixtures, especially those involving synthetic multicomponent solvents, are scarce. This study provides comprehensive LLE measurements of bitumen and a multicomponent synthetic solvent (n-pentane + n-hexane + n-heptane + cyclo-hexane + toluene) conducted under controlled equilibrium conditions at temperatures of 295 to 352 K, solvent concentrations up to 70 wt% at 1.291 MPa. Application of common correlation used in the construction of solvent-aided process fluid models exhibited average absolute relative deviations (AARDs) of 0.37 % for density and 8.87 % for viscosity. We identified the boundaries marking the shift from homogenous single-phase liquid to two-phase (LLE) states, which occurs within the synthetic multicomponent solvent concentration range of 50 to 60 wt%. We also successfully constructed calibration curves to measure solvent concentrations in both phase regions. The molecular weight distribution and saturates, aromatics, resins, and asphaltene (SARA) fractionation of both liquid phases were determined, highlighting that the heavy liquid phase is primarily asphaltene (∼46 wt%). The insights gained from the measurements and analysis find applications in designing and optimizing solvent-assisted thermal recovery processes for bitumen extraction.