The following manuscript presents a comprehensive investigation regarding the influence of electrospinning parameters on fiber quality and mechanical properties of nanofibrous poly(amino acid) meshes. At first, we examine parameters including: solvent options, polymer concentrations, collector speed and distance, voltage, needle sizes and flow rates to prepare fibrous scaffolds based on polysuccinimide. The main objective was to attempt and decrease the fiber diameter as much as possible while not reducing the fiber quality. After that mechanical properties of the meshes were investigated, we demonstrate two possible methods to reinforce them: mechanically induced alignment of the fibers and multilayer compression. Characterization methods include a solubility study, viscosity and conductivity measurements, ATR‐FTIR spectroscopy, scanning electron microscopy, and mechanical uniaxial test. Fiber size was successfully reduced from 615 to 280 nm without any quality aberrations. Mechanical performance not only improved almost three‐fold, but was also enhanced in two directions due to the multilayer composition. With these optimizations, the PSI mesh now possess favorable features for biomedical application according to the relevant literature.