It needs to assemble the industrial CNT powders into macroscopic porous surface composite to utilize the surface properties of CNTs, as well as to prevent them entering into environments. We demonstrate a method to fabricate the surface composites from CNTs and polyvinylpyrrolidone (PVP) by electrospinning, where CNTs distribute firmly and mainly on the surface PVP nanofibers. The CNTs/PVP surface composites have high pore volume of similar to 10 cc/g and remarkable CNTs load of 98%. Thus the surface composites show high oil adsorption capacity of 0.9 similar to 1.1 g/cm(3). It can absorb more oil than commercial sponges due to the surface composite swells after absorbing oil. It shows attractive potential application of the CNT/PVP surface composite in oil spill cleanup.