Electrospun carbon fiber electrodes showing high performance for bio-electrochemical applications were developed. Easy to handle and manipulate aligned and unaligned carbon fibers with a mean diameter of (330 +/- 50)nm were synthesized through an electrospinning technique. Electrical resistivity measurements, which are a challenge that has not been much explored in the case of fibrous materials, were realized through two different techniques, and a study of contact resistances between electrical clips and the carbon fibers was performed. To target the creation of a bioelectrode, carbon fibers were characterized electrochemically by cyclic voltammetry. After being modified with the enzyme laccase, its response to oxygen electroreduction was studied. Aligned fibers present a cathodic current that is 30% higher than that of randomly distributed fibers. Overall, the results show that aligned fibers are more appropriate for bio-electrochemical applications when exploiting anisotropic spatial organization.