•A copper foam with negative charge and tortuous permeation channels was prepared.•The separation efficiency of the foam for dyes such as MB was as high as 99.93%.•Due to the large pore size, the permeate flux of the foam reaches 1671 L m-2h−1.•The foam has selective separation capability for mixed cationic dye wastewater.•Molecular dynamics simulations were used to explain the separation mechanism. Rapid and efficient separation of dyes from water is a formidable challenge due to the trade-off between separation selectivity and permeability. Here, a novel superhydrophilic copper foam (CF) enabling the rapid and efficient filtration of cationic dyes from water is reported. The fabrication involves brushing a coating consisting of attapulgite (APT), poly(vinyl alcohol) (PVA), TiO2 and glutaraldehyde (GA) onto copper foam and then heating. The obtained copper foam (CF-PVA/GA@APT/TiO2) is superhydrophilic and negatively charged with dye adsorption capability. The interconnected cage-shaped porous structure endows the foam with long tortuous permeation channels and large pore size. It is able to separate various cationic dyes with a separation efficiency reaching to 99.93 % and a permeation flux up to 1671 ± 189 L m-2h−1 under gravity. Furthermore, the CF-PVA/GA@APT/TiO2 can realize the selective separation and recovery of various cationic dyes from rhodamine B (RhB)-mixed dye solutions. Molecular dynamics-based computational modeling and experimental studies revealed that the interaction energy between the surface of CF-PVA/GA@APT/TiO2 and methylene blue (MB) is much stronger than that of the former and RhB, leading to adsorption of MB in the permeation channel, while RhB gradually migrates through the permeation channel and passes through the channel with water. The tortuous permeation channels of CF-PVA/GA@APT/TiO2 increase the contact area and absorption opportunities for cationic dye molecules on the surface, and its large pore size maintains the filtration flux. These properties provide the as-prepared foam with excellent potential applicability for industrial dye wastewater treatment.