In order to effectively promote the treatment of pollution containing organics or crude oil, many oil‐absorbing materials were explored. However, most of them were synthetic polymers, which was difficult to be decomposed and easily cause secondary pollution. In this study, zein and sodium alginate (SA), two cheap natural polymer materials, were used as eco‐friendly and biodegradable biomass materials; a novel porous biomass‐based sponge (ZS‐PBSp) was synthesized. Then, by impregnating with SiO2 nanoparticle (nano‐SiO2) and octadecanethiol (OCT), the modified porous sponge (ZSSiOsp) was obtained. ZSSiOsp was characterized by scanning electron microscopy (SEM), infrared (IR), X‐ray diffraction (XRD) and thermogravimetric analysis (TGA) and applied to adsorb organics, such as organic solvents, petroleum products and cooking oil. It indicated that the surface of ZSSiOsp was rough, and its water contact angle (WCA) increased to 131.5°. ZSSiOsp effectively adsorbed organics, its absorption capacity got to 115.7% for chloroform and 77.6% for rapeseed oil, respectively. It also effectively separated oily substances from oil–water mixture. In summary, the obtained ZSSiOsp was an eco‐friendly material for oil absorption and separation, which was a kind of promising candidate in water treatment and environmental protection.