Composite electrolytes consisting of methyl-capped poly(ethylene glycol) oligomer (Mw approximate to 250), lithium bis(trifluoromethylsulfonyl)imide (Li: O = 1: 20), and fumed silica were investigated. In particular, the effects of fumed silica-surface chemistry and weight percentage in the composite on cycling behavior of Li/electrolyte/Li, Li(Ni)/electrolyte/Li, and Li/electrolyte/metal oxide cells were studied. Four types of fumed silicas with various surface groups were employed, A200 (native hydroxyl groups!, R805 (octyl-modified), R974 (methyl-modified), and FS-EG3 (ethylene oxide-modified). The presence of fumed silica enhances lithium cyclability by reducing the interfacial resistance and cell-capacity fading, regardless of surface chemistry. However, the extent of the enhancing effect of fumed silica strongly depends on its surface chemistry, with the largest effect seen with A200 and the least effect seen with FS-EG3. Increasing fumed silica weight fraction intensifies the stabilizing effect.