By combining the electrospinning method advantages (high surface-to-volume ratio, controlled morphology, varied composition and flexibility for the resulting structures) with the electrical activity of polyaniline, a new core-shell-type material with potential applications in the field of artificial muscles was synthesized. Thus, a poly(methylmetacrylate) solution was electrospun in optimized conditions to obtain randomly oriented polymer fiber webs. Further, a gold layer was sputtered on their surface in order to make them conductive and improve the mechanical properties. The metalized fiber webs were then covered with a PANI layer by in situ electrochemical polymerization starting from aniline and using sulphuric acid as oxidizing agent. By applying a small voltage on PANI-coated fiber webs in the presence of an electrolyte, the oxidation state of PANI changes, which is followed by the device colour modification. The morphological, electrical and biological properties of the resulting multilayered material were also investigated.