Electrospun fibers with nano-/micro-scale porous structures were successfully fabricated from polymer solutions that contained suspended micro-/nano-size salt particles of sodium chloride or calcium carbonate, which were subsequently removed through a leaching process after electrospinning. It was found that the size and dispersion of the salt particles had significant effects on the pore size and pore distribution in the resulting electrospun fibers. Using sodium chloride salt particles in the electrospinning process should not induce any residual toxicity in the resulting porous fibers. Therefore, this approach provides a very simple and versatile method in the fabrication of electrospun fibers that have secondary nano-/micro-scale porous structures, which are desirable in many important biomedical applications including tissue engineering and controllable drug release.