In this work, a TiO2/g-C3N4 photocatalytic coating is built on cotton fabrics with a simple layer-by-layer (LBL) self-assembly strategy in which TiO2 and g-C3N4 are alternately assembled on cotton fabrics via electrostatic attraction. The fabrics, as support, disperse TiO2/g-C3N4 powder photocatalyst to expose more active sites. The fabrics also act as an adsorbent to boost the pollutants capture. Consequently, the coated fabrics exhibit an outstanding photocatalytic property applicable for degradation of both liquid rhodamine (RhB) and gaseous toluene pollutants. The fabric with seven bilayer coatings shows the best for RhB decomposition with degradation rate of 92.5%. Over 90% toluene could be eliminated by the photocatalytic coating under simulated sunlight irradiation. Besides, the coating fabrics show excellent stability and reusability.