The present chitosan-based superfine fiber invention relates to compositions, formulations, and processes that result in numerous significant advantages for the production and use of superfine fiber bioactive matrices in biomedical applications. The present invention relates to superfine, chitosan-based fibers, wherein the chitosan-based fibers have a percentage chitosan content of at least about 20% w/w, and highly conformable and compliant matrices comprising such fibers, processes for their production, and related formulations. The superfine chitosan-based fibers of the invention preferably include microfibers with diameter less than or equal to about 10 microns and micron and submicron fibers that are about 2 microns and less.