Two-dimensional siloxene sheets are an emerging class of materials with an eclectic range of potential applications including electrochemical energy conversion and storage sectors. Here, we demonstrated the dehydrogenation/dehydroxylation of siloxene sheets by thermal annealing at high temperature (HT) and investigated their supercapacitive performances using ionic liquid electrolyte. The X-ray diffraction analysis, spectroscopic (Fourier transform infrared, laser Raman, and X-ray photoelectron spectroscopy) studies, and morphological analysis of HT-siloxene revealed the removal of functional groups at the edges/basal planes of siloxene, and preservation of oxygen-interconnected Si 6 rings with sheet-like structures. The HT-siloxene symmetric supercapacitor (SSC) operates over a wide potential window (0-3.0 V), delivers a high specific capacitance (3.45 mF cm -2 ), high energy density of about 15.53 mJ cm -2 (almost 2-fold higher than that of the as-prepared siloxene SSC), and low equivalent series resistance (compared to reported silicon-based SSCs) with excellent rate capability and long cycle life over 10 000 cycles.