This review aims to overview state-of-the-art progress in the collaborative work between theoretical and experimental scientists to develop advanced electrolytes for Na-ion batteries (NIBs). Recent investigations were summarized on NaPF6 salt and fluoroethylene carbonate (FEC) additives in propylene carbonate (PC)-based electrolyte solution, as one of the best electrolytes to effectively passivate the hard-carbon electrode with higher cycling performance for next-generation NIBs. The FEC additive showed high efficiency to significantly enhance the capacity and cyclability of NIBs, with an optimal performance that is sensitive at low concentration. Computationally, both microscopic effects, positive and negative, were revealed at low and high concentrations of FEC, respectively. In addition to the role of FEC decomposition to form a NaF-rich solid electrolyte interphase (SEI) film, intact FECs play a role in suppressing the dissolution to form a compact and stable SEI film. However, the increase in FEC concentration suppressed the organic dimer formation by reducing the collision frequency between the monomer products during the SEI film formation processes. In addition, this review introduces the Red Moon (RM) methodology, recent computational battery technology, which has shown a high efficiency to bridge the gap between the conventional theoretical results and experimental ones through a number of successful applications in NIBs.