Highly efficient and low-cost treatment of waterworks sludge and oil-containing Cr (Ⅵ) wastewater in one way is a challenge in the field of water treatment. Herein, a waste-control-waste strategy was proposed to fabricate a functionalized waterworks sludge-based Zn–Al layer double oxides material (Zn–Al LDOs/WS) for simultaneously separating Cr (Ⅵ) and oil. During the column separation process, due to the superhydrophilic/underwater superoleophobicity of Zn–Al LDOs/WS and the memory effect of LDHs, Cr (Ⅵ) will be stabled in the filter layer by electrostatic attraction and surface complexation between the Zn–Al LDHs/WS and Cr (Ⅵ), and the small oil droplets will coalesce into big oil droplets that be blocked in the separation column, thus achieving simultaneous separation. The Zn–Al LDOs/WS with hierarchical porous structure exhibit excellent simultaneous separation efficiency for Cr (Ⅵ) (99.69%) and oil (99.24%), and high separation flux (1063 L m−2 h−1). In addition, the separation efficiency and flux can be flexibly controlled by adjusting the filter layer thickness. The Zn–Al LDOs/WS also display strong acid and alkali resistance (pH 1–11), wide applicability range of initial Cr (Ⅵ) concentration (5–200 mg/L) and outstanding anti-interfering ion ability (Cl−, HCO3−, SO42−, NO3−, H2PO4−, CO32− and F−) in Cr (Ⅵ) and oil separation. Therefore, this work can not only improve treatment efficiency and save costs through simultaneous separation, effectively treat solid waste and complex wastewater, but also provide a theoretical basis for the design and application of functional materials derived from waste sludge.