The present article describes our recent research works on the electrospinning of natural and bio-related polymeric materials. A synthetic poly(amino acids), poly(γ-benzyl-L-glutamate) (PBLG) and two natural polysaccharides, chitosan and cellulose, have been successfully spun into submicro- or nano-scaled fibers, which can be obtained as “electrospun non-woven fabrics (ESNWs)”. The major topics are (i) relationship between the chain conformation of PBLG in the pre-spun solution and the resulting post-spun morphology and mechanical property of PBLG-ESNWs, (ii) direct electrospinning of chitosan solution, preparation of the nanofibers, and post-spun treatment of the chitosan-ESNWs, with respect to the polymer chemical properties, and (iii) preparation of cellulose-ESNWs composed of the nano-scaled fibrous network and biomedical application as drug-carrier and releasing materials. Finally, technological aspects of the industrial application of these ESNWs were discussed, enclosing with perspectives for the future research subjects and possible applications.