Carbon xerogels have generally low textural properties compared with carbon aerogels and carbon cryogels since the gas-liquid interface produces a capillary force in small pores. In this work, the templated carbon xerogels (TCXs), using resorcinol-formaldehyde (RF) and cotton fibres (CFs) as a hard template, were synthesized by CF removal from CF/RF composite hydrogels by sulphuric acid treatment. The TCX precursors were exchanged by t-butanol, dried by evaporation drying, and carbonized at high temperature. Scanning electron microscope images and Hg intrusion data confirm that TCXs possess macropores whose walls are the carbon xerogel scaffold. Their nitrogen adsorption and desorption isotherms also support that TCXs have micropores and mesopores. The quantities of micropores, mesopores and macropores are improved with the increase of CF utilization. X-ray diffraction allows us to know that TCXs have a graphitic structure. The intensity of D to G from the Raman spectra is also investigated. Display omitted •TCXs prepared by using H2SO4 treatment have micropores, mesopores, and macropores.•The carbon xerogel scaffold acts as the macropore wall.•The greater the CF utilization, the greater the textural properties of TCXs.•The macropores are created by CF removal from the CF/RF composite hydrogels.•The low R/W ratio, 0.25 g/cm3, enhances the increase of micropores and mesopores.