Triboelectric nanogenerators (TENGs) are attractive research since their discovery, and various strategies are developed in order to improve their output performance. Recently, the ionic gel has been attracted to the TENGs field, but it typically has limited power output and durability. Here, a strategy of adding silica‐supported ionic liquid to the polymer (solid polymer electrolyte) as a triboelectric material is reported. This method of tribo‐material is created using a straightforward sol–gel process, resulting in a versatile, stable, durable, and high power output performance. When coupled with spin‐coated polydimethylsiloxane as negative material provides an output voltage of 248 V, a current density of 61.5 mA m−2 and power density of 5.2 W m−2 which is sufficient to light up 160 white light‐emitting diodes. Comparatively, pristine poly(vinyl alcohol) (PVA) film merely harvests 125 V, 26.5 mA m−2, and power of ≈2.48 W m−2. The high output is attributed to the silica precursor in the membrane, which makes more –OH groups of PVA to form long chains network with other oxygen of alkoxy groups through hydrogen bonding and also the presence of nitrogen groups of imidazolium. This work thus expands the enhancement of the positive material utilized for triboelectric nanogenerators with high possibility. [ABSTRACT FROM AUTHOR]