A novel clean method to synthesis a composite monolith was developed. Given its amphiphilic property, UiO-66 can emulsify water and CO 2 to format a high internal phase emulsion (HIPE) under certain conditions. These UiO-66-emulsified Pickering HIPEs can be used as templates to prepare interconnected macroporous MOF/polymer composite monoliths. The effects of UiO-66 amount, cross-linking agent concentration, and CO 2 -water ratio on UiO-66/PAM structures were investigated. Then, the as-synthesized MOF/PAM composites were characterized by TGA, XRD, SEM, and FT-IR analyses, as well as rheological and DMA measurements. The results indicated that the composites are interconnected with hierarchical pores, and the diameter of the voids is 10-50 μm. The directly prepared monoliths exhibited relatively high stresses at 82% strain and recovered their shape quickly. The adsorption capacity of the composites for methylene blue (MB) is 50 mg g -1 at a faster adsorption rate. The monoliths also exhibit underlying applications in edible oil-water separation.