Water pollution caused by oily and textile wastewater has become a global concerned problem. Wastewater typically contains organic dyes, oil-water emulsions and other pollutants. Hence, it is crucially important to prepare materials that can separate oil-water mixtures/emulsions and adsorb organic dyes. In this work, the semi-encapsulated MOF-5 modified coal-based fiber membranes were prepared by one-step electrospinning method. The modified membrane exhibits superhydrophilic/underwater superoleophobic, excellent stability, high flux (oil-water mixture flux = 8861 L m-2 h-1, oil-in-water emulsion flux = 504 L m-2 h-1) and commendable separation efficiency (98.7%, 99.9%). The membrane could achieve a highly efficient dye absorption (94.9%). The semi-encapsulated construction makes the MOF-5 well protected and the active site can be greatly exposed, leading to significantly improved stability and adsorptive properties. The MOF-5 modification renders the surfaces hydrophilic and increases the roughness which improves water flux and wettability. The composite material provides a new idea for the separation of oil-water mixtures/emulsions and the adsorption of organic dyes.