Often, to address the challenges of the lithium ion battery active materials in terms of poor cycling performance, interface instability, severe volume changes and incompatibility with the carbonate-based electrolyte, different electrolyte components are combined together. Although a synergistic effect would bring up the advantages of different electrolyte constituents, their interaction is sometimes neglected. In this study, we report on the interaction of two well-known electrolyte additives, i.e. 1,3,2-dioxathiolane 2,2-dioxide (DTD) and fluoroethylene carbonate (FEC) and the effect that tris(trimethylsilyl)borate (TMSB) play on the chemical and electrochemical stability of the investigated cell system, i.e. LMR||μ-Si cell chemistry. Comprehensive electrochemical characterizations with the support of advanced analytical methods, provide a detailed “mechanism of action” of DTD and FEC in the electrolyte formulation. On the other side, we show that the presence of 1 wt.% of TMSB in the baseline electrolyte, suppresses the roll-over effect observed for the LMR-cathode, although, TMSB has a less pronounced effect on the μ-Si electrode. However, the combination of TMSB with both DTD and FEC results in improved long-term cycling and stabilizes the electrolyte formulation. Such a behavior can also arise from the logical choice of the electrolyte additives by considering their individual interactions even before their effect on the cell chemistry.