Non-smooth surface of a nano or micro-scale fiber has an extremely large surface area and a tremendously high surface energy (geometric potential). This paper focuses on the formation mechanism of fabrication of a non-smooth surface by electrospinning through controlling solvent evaporation and nanoscale adhesion of nanoparticles on the surface. Poly(vinylidene fluoride), multi-wall carbon nanotubes and a binary solvent system are adopted in the experiment to elucidate how to fabricate nanoscale porous nanofibers and lotus-surface-like nanofibers. A nanoparticle's vibration near its equilibrium is also discussed, which also affects greatly the surface morphology.