Versatile and ductile cotton fabrics with extraordinary electrical and robust ultraviolet protective properties can be facilely prepared by depositing graphene doped poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) and chitosan upon fabric substrate via layer-by-layer electrostatic self-assembly approach in this paper. The PEDOT: PSS as polyanion was doped with graphene nanosheet (1 wt.%) by solution mixing followed by alternative deposition with chitosan as polycation on the surface of cotton fabric. The morphology and structure of the resultant fabrics were characterized by SEM, AFM and ATR–FTIR and dyeing color depth (K/S value), the electrical and ultraviolet protective properties were also evaluated. As expected, dyeing color depth (K/S value) illustrated regular and identifiable “odd–even” changes indicating the variation of surface molecular layer of the alternate deposition of PEDOT: PSS and chitosan layer. Furthermore, electrical resistivity of the six-layer deposited fabric could reach to 2.29 Ω m, decreasing more than eight orders of magnitude than the control fabric, Meanwhile, such fabric could also perform ultrastrong ultraviolet protective ability with a maximum UPF value of 312, which was up to 30-fold increment of control fabric (UPF = 9.37). In addition, the LbL fabric possessed excellent washing durability even after ten times water laundering.