Electrospun materials have been proposed for application for gas filtration, drug carriers, and tissue engineering. The surface morphology of electrospun fibers is the key for consideration for the above applications, such as pore size on the fiber surface, surface area, and roughness. In this work, we investigated the influence of polymer/solvent properties on soluble polyimide (PI) fibers. The studied PIs included three fluorinated aromatic polyimides containing naphthalene pendant groups. By using various solvents we adjusted the size, shape, and structure of the fibers. As a result, PI electrospun fibers could be achieved with width around 10 μm. The rough and smooth surface morphologies were studied by scanning electron microscopy (SEM). Surface wettability of the electrospun fiber membranes were characterized by contact angle measurement. The contact angles on the electrospun PI fiber mats for water and glycerol were in the range of 137.6°–144.5° and 139.1°–143.6°, respectively. Moreover, the rough fiber surface could make the electrospun fiber membrane possess good adhesive force for liquids. The results suggest that we could widen the application of electrospun membranes through controlling the fiber morphology.