To allow stable cycling of layered nickel-rich cathode material at high voltage, silyl-functionalized dimethoxydimethylsilane is proposed as a multi-functional additive. In contrast to typical functional additive, dimethoxydimethylsilane does not make artificial cathode-electrolyte interfaces by electrochemical oxidation because it is quite stable under anodic polarization. We find that dimethoxydimethylsilane mainly focuses on scavenging nucleophilic fluoride species that can be produced by electrolyte decomposition during cycling, leading to improving interfacial stability of both nickel-rich cathode and graphite anode. As a result, the cell cycled with dimethoxydimethylsilane-controlled electrolyte exhibits 65.7% of retention after 100 cycle, which is identified by systematic spectroscopic analyses for the cycled cell.