Skin injuries are an urgent health issue, which raises a great concern in the clinic. Although numerous strategies have been proposed to fabricate skin substitutes for treatment of wounds over the past several decades, fabricating an ideal skin substitute to replace the damaged one can still be a problem. In this study, a novel biomimetic 3D composite skin scaffold is fabricated by combining electrohydrodynamic (EHD) jetting, electrospinning, and coating techniques. Here, the first polycaprolactone (PCL) porous structure is produced by the EHD jetting. Next, the second polylactic acid (PLA) membrane consisted of nanoscale fibers is prepared on the PCL porous structure via the electrospinning. The PCL porous structure and PLA fibers membrane can mimic the dermis and epidermis layer, respectively. Furthermore, gelatin is used as coating solution to enhance the biocompatibility of the scaffold. The structure and morphology of the fabricated scaffolds are analyzed, and the mechanical properties are investigated as well. Moreover, the in vitro and in vivo experiments demonstrate the biocompatibility of the materials and the fabrication process. In conclusion, these results demonstrate that the composite scaffold is effective and holds great potential for skin regeneration in the clinic.