Methods are provided for functionalizing a macroscopic film comprised of nanoscale fibers by controlled irradiation. The methods may include the steps of (a) providing a nanoscale fiber film material comprising a plurality of nanoscale fibers (which may include single wall nanotubes, multi-wall nanotubes, carbon nanofibers, or a combination thereof); and (b) irradiating the nanoscale fiber film material with a controlled amount of radiation in the open air or in a controlled atmosphere. The step of irradiating the nanoscale fiber film material is effective to functionalize the plurality of nanoscale fibers. Irradiated nanoscale fiber films are also provided having improved mechanical and electrical conducting properties.