Electrospinning has become a versatile technique to produce continuous fibers with micrometer and nanometer diameters from a variety of polymer solutions or melts. However, not of all polymers can form fiber via this electrospinning approach. For example, polystyrene (PS) at lower temperature and low concentration, and in high volatile solvent didn’t form fibers but beads structure by electrospinning method. In this work, PA6 was used as an additive of PS system to improve the electrospining behavior of PS. The results show that the bead-free PS fiber could be produced once the introduction of PA6. In order to further decrease the amount of PA6, a random copolymer of styrene (St) and 3-isopropenyl-α,α-dimethylbenzene isocyanate (TMI), denoted as PS-co-TMI, was used to as the reactive compatibilzer of PS/PA6 blend. A bead-free PS fibers could be produced even in the low ratio of PS/PA6-TFAA with addition of PS-co-TMI as reactive compatibilizer.