Porous EC/PVP fibers were fabricated by centrifugal spinning while nonporous fibers were obtained in electrospinning. The porous EC/PVP fibers showed great high specific surface area and contact angle. The mechanism was established to clarify the morphology change between centrifugal-spun fibers and electrospun fibers. The centrifugal spinning is meaningful for the rapid and large-scale fabrication of porous fibers.