Electrospun polymer fibers are gaining importance because of their unique properties and applications in areas such as drug delivery, catalysis, or tissue engineering. Most studies to control the morphology and properties of electrospun polymer fibers focus on changing the electrospinning conditions. The effects of post-treatment processes on the morphology and properties of electrospun polymer fibers, however, are little studied. Here, the effect of thermal annealing on the surface properties of electrospun polymer fibers is investigated. Poly(methyl methacrylate) and polystyrene fibers are fist prepared by electrospinning, followed by thermal annealing processes. Upon thermal annealing, the surface roughness of the electrospun polymer fibers decreases. The driving force of the smoothing process is the minimization of the interfacial energy between polymer fibers and air. The water contact angles of the annealed polymer fibers also decrease with the annealing time.