Entire carbon nanofiber mats (carbon nanofiber paper) based on polyacrylonitrile pyropolymer composite were prepared by the preliminary oxidation (stabilization) of the initial polymer at 250–350°C in air and following pyrolysis at 800–1200°C under vacuum. The mats were tested as cathodes in a fuel cell on polybenzimidazole membrane. Properties of the pyropolymers which were obtained by polymer carbonization could be significantly changed by the addition of specific additives to polyacrylonitrile and also by changing thermal treatment. Particularly, the addition of Ketjen Black® or Vulcan® XC72 carbon blacks and polyvinyl pyrrolidone during electrospinning step resulted in increase of material electrical conductivity and inner porosity, which is important for improving fuel cell performance. Depending on oxidation and pyrolysis temperature, the physical properties of platinated carbon nanofiber paper and the efficiency of a fuel cell on polybenzimidazole membrane significantly change.