This work presents a simple and reliable method for directly generating polyvinylidene fluoride (PVDF) nanofibers with secondary surface morphology (e.g., porous surfaces, rough surfaces, grooved surfaces, and interior porosity) by using single/binary solvent systems and relative humidity. We clarified the mechanisms responsible for the formation of these morphologies by systematically exploring the molecular interactions among the polymer, solvent(s), and water vapor. Our results proved that the formation of secondary surface morphology needed the presence of water vapor, a non-solvent of the polymer, at an appropriate level of relative humidity. The formation of secondary surface morphology was dependent on the speed of evaporation of the solvent(s) (ACE, DMF, and their mixtures), as well as the inter-diffusion and penetration of the non-solvent (water) and solvent(s). The results of N-2 physical adsorption-desorption isotherms showed that the macro-porous fibers (> 300 nm) exhibited the highest specific surface area of 2331 +/- 4.30 m(2)/g and pore volume of 0.0695 +/- 0.007 cm(3)/g, enabling the high oil absorption capacities of 50.58 +/- 5.47 g/g, 37.74 +/- 433 g/g, and 23.96 +/- 2.68 g/g for silicone oil, motor oil, and olive oil, respectively. We believe this work may serve as guidelines for the formation of different structures of macro-porous, rough, and grooved nanofibers with interior porosity through electrospinning.