Fluorine-rich nanoporous carbons with tunable porosity and F content have been successfully synthesized from a silane precursor using a solution-based F doping method. The F-rich carbon surface with higher polarity provides stronger affinity and wettability for the organic electrolyte, which is for the first time demonstrated though Gauss computational calculation between F-carbon surface and organic electrolytes. The optimized F-rich nanoporous carbon manifests a high specific capacitance of 168Fg−1 in a symmetric cell with excellent retention at high rates and upon prolonged 10,000 cycles.