Polyacrylonitrile (PAN) fibre-supported carbon (C)-doped TiO2 (PCT) was fabricated by electrospinning C-doped TiO2/PAN/N,N-dimethylformamide mixtures. C doping was found to be a promising method for enabling visible photoactivation of TiO2 using graphite and PAN fibres as carriers. The fibrous PAN not only facilitated visible light-activated harvesting of TiO2 but also enabled the incorporation of C into the TiO2 lattice during the preparation process. Such composite fibres endowed TiO2 with high photocatalytic activity, and they were utilised to degrade toluene from interior wall paints with excitation at 440 nm. Given the maximum removal efficiency of 96.8% within 1 h, the developed photocatalysts can be considered to have paint hazard remediation properties.