Three-dimensional(3D)carbon networks have been explored as promising capacitive materials thanks to their unique structural features such as large ion-accessible surface area and interconnected porous networks,thus enhancing both ions and electrons transport.Here,sustainable bacterial cellulose(BC)is used both precursor and template for facile synthesis of free-standing N,S-codoped 3Dcarbon networks(a-NSC)by the pyrolysis and activation of polyrhodanine coated BC.The synthesized a-NSC shows highly conductive interconnected porous networks(24S·cm^(-1)),large surface area(1 420m^2·g^(-1))with hierarchical meso-microporosity,and high-level heteroatoms codoping(N:3.1%in atom,S:3.2%in atom).Benefitting from these,a-NSC as binder-free electrode exhibits an ultrahigh specific capacitance of 340F·g^(-1)(24μF·cm^(-2))at the current density of 0.5A·g^(-1)in 6MKOH electrolyte,high-rate capability(71%at 20A·g^(-1))and excellent cycle stability.Furthermore,the assembled symmetrical supercapacitor displays a much short time constant of 0.35sin 1MTEABF4/AN electrolyte,obtaining a maximum energy density of 32.1W·h·kg^(-1 )at power density of 637W·kg^(-1).The in situ multi-heteroatoms doping enables biocellulose-derived carbon networks to exploit its full potentials in energy storage applications,which can be extended to other dimensional carbon nanostructures.