With increasing oil spill accidents, the development of effective and low-cost adsorbents with good hydrophobicity is highly desirable. To cope with the clean-up of oil spill, a hydrophobic adsorbent was synthesized by electrospinning using inexpensive raw materials. By ingeniously combining melamine with polyacrylonitrile (PAN) as well as SiO2 nanoparticles, a novel composite nanoadsorbent named SiO2@MUF/PAN nanofibrous membrane was prepared and characterized. The adsorbents were conducted based on uniform nanofibre networks and were abundant with narrow slit-like pores, which are significant for the retention of oil and organic solvents. The hydrophobicity of the as-prepared membranes was enhanced with an increasing amount of SiO2, and the highest water contact angle was 128.3 degrees. Furthermore, the combination of SiO2 and melamine increased the thermal stability of the membranes. With the unique pore structures and hydrophobicity, the membranes were able to selectively remove not only oil but also organic solvents from water surface. The adsorption capacities of the membranes with SiO2 nanoparticles (0.9wt%) were the highest and that for peanut oil, diesel, pump oil and engine oil were 19.09, 13.12, 18.48 and 22.67gg(-1), respectively, while that for organic solvents ranged from 12.92 to 22.16gg(-1). After 10 adsorption-regeneration cycles, the adsorption capacity was still around 35% of the initial value. Due to its high oil adsorption capacity, excellent reusability and the cost-effective hydrophobic, SiO2@MUF/PAN have a great potential for oil spill clean-up.