Wastewater from industrial processes usually contains insoluble oil slick and soluble organic dyes. Thus, it is of great significance to design novel materials for the simultaneous oil/water separation and dye removal in efficient wastewater purification. In this study, polydopamine (PDA) was firstly self-polymerized on PET textile to obtain PET@PDA. Then, a honeycomb-like Co-Al LDH layer grafted on the PET@PDA via a hydrothermal method to fabricate the PET@PDA@LDH. Finally, TiO2 nanoparticles were intercalated into the LDH nanosheet layer crosslinking with polyethyleneimine (PEI), obtaining PET@PDA@LDH@P-TiO2 membrane. By adjusting their hierarchical architecture and surface chemistry, PET@PDA@LDH@P-TiO2 membrane exhibited dual superlyophobicity of underwater superoleophobicity and underoil superhydrophobicity. Combining its unique superwetting property and porous structure, PET@PDA@LDH@P-TiO2 membrane could be applied for the gravity-driven on-demand separation of various oil/water mixtures. More importantly, the PET@PDA@LDH@P-TiO2 membrane exhibited good absorption and photocatalytic degradation performances to various organic dyes under UV illumination. Thus, without complicated operations and toxic chemicals, the dual-functional fabric shows great potential applications in complex oily wastewater remediation.