Two samples of commercial conducting carbon black and the carbon generated in situ during LiFePO4/C composite synthesis from citric acid are studied, with the aim of finding out whether carbon from the composite can fulfil the same function as carbon black in the electrode blend for a Li-ion battery. For this purpose, the carbon samples are analyzed by several techniques, such as X-ray diffraction, Raman spectroscopy, transmission electron microscopy, granulometry, BET specific area and conductivity measurements. Different cathode compositions and component proportions are tested for pellet and cast electrodes. Electrochemical results show that a moderate reduction of commercial carbon black content in both kinds of cathodes, by adding more LiFePO4/C composite, enhanced the electrochemical behaviour by around 10%. In situ generated carbon can partially replace commercial conducting carbon black because its high specific surface probably enhances electrolyte penetration into the cathode, but it is always necessary to maintain a minimum amount of carbon black that provides better conductivity in order to obtain a good electrochemical response.