Highly aligned ultrafine fibers of Poly (amide-co-imide) PM (torlon)/Poly (trimellitic anhydride chloride-co-4, 4'-methylene dianiline) (PTACM) blends have been prepared by using mechano-electrospinning. Employing a mixed solvent system of DMSO and THE alongwith water coagulation bath as a medium, continuous fibers with improved mechanical properties have been obtained. The continuity of the fibers is strongly dependent on the solvent mixing ratio of DMSO and THF (6:4). Continuous fibers with the most uniform diameter are obtained when a 30 % of PAT and PTACM (1:1) resins by weight is used in the blending solution. The aligned fibers are further coated with silver nanoparticles using a one-step process by passing the electrospunned fibers through PEG solution and a silver precursor solution followed by reduction in a continuous process. The advantage of our method lies in a uniform silver coating on a single fiber that can be coated continuously on a larger length scale (similar to Km). The mechanical properties of these fibers are dramatically improved after their alignment. Better electrical conductivity is obtained for these fibers after they are coated with silver nanoparticles. The highly aligned silver decorated fibers utilizes a novel electroless continuous process using Polyethylene glycol (PEG), which shows good binding properties and can be used for various bio and electronic applications.