A major challenge in oil/water separation is the processing of surfactant-stabilized emulsions from the water medium. One of the feasible schemes of emulsion separation is the porous melamine sponge coupled with functional particles. Here, we proposed a novel superhydrophobic metal-organic framework (MOF)-based sponge for water-in-oil emulsion separation. The porous melamine sponge was combined with poly(dimethylsiloxane) (PDMS)-coated hydrophobic SiO2 and UiO66-OSiR particles were prepared for demulsification via the one-step dipping method for the first time. The PDMS@SiO2@UiO66-OSiR sponge revealed excellent superhydrophobicity at a water contact angle of 160.7° and superlipophilicity at an oil contact angle of 0°. Compared with the pristine melamine sponge, the size-controllable PDMS@SiO2@UiO66-OSiR sponge could separate stabilized water-in-oil emulsions with ultrahigh separation efficiency (>98.64%) and high flux (e.g., 970 L·m-2·h-1). Meanwhile, the PDMS@SiO2@UiO66-OSiR sponge exhibited superior durability and mechanical reusability. Under harsh conditions such as strong acid and alkali, organic solvent corrosion, etc., all water contact angles of the PDMS@SiO2@UiO66-OSiR sponge were over 152°. Furthermore, the stress decreased by 5% when the sponge was subjected to 10 loading/unloading compression cycles at a constant strain of 60%. These results demonstrate that the PDMS@SiO2@UiO66-OSiR sponge can efficiently separate water-in-oil emulsions through its adjustable porous structure coupled with demulsification and hydrophobic particles. This study provides a step forward in developing a feasible strategy for the MOF-based sponge for emulsion separation.