Superhydrophilic/underwater superoleophobic materials for the separation of oil-water emulsions by filtration have received much attention in order to solve the pollution problem of oil-water emulsion. In this paper, a fence-like structure on the surface of CNF/KGM (Konjac Glucomannan) materials by a simple method using CNF instead of metal nanowires was successfully developed based on the hydrogen bonding of KGM and CNF. The resulted organic CNF/KGM materials surface has outstanding superhydrophilic (WCA = 0 degrees) in air and superoleophobicity (OCA >= 151 degrees) in water, which could separate oil-water mixtures with high separation efficiency above 99.14 % under the pressure of the emulsion itself. The material shows good mechanical properties because of the addition of CNF and has outstanding anti-fouling property and reusability. More importantly, the material can be completely biodegraded after buried in soil for 4 weeks since both of KGM and CNF are organic substances. Therefore, it may have a broad application prospect in the separation of oil-water emulsion because of its outstanding separation properties, simply preparation method and biodegradability.