A composite using polyaniline (PAni) as the conducting polymer and silica sol-gel as the host matrix was prepared by the template method. To evaluate the electrochemical performance of the PAni/silica composite, PAni films were synthesized under the same conditions, directly on ITO substrates and the results were compared. Cyclic voltammetry, impedance spectroscopy, charge-discharge cycles and lifetime tests were done in organic medium. The PAni/silica composite showed excellent performance in all of the tests. This composite may therefore be useful for cathodes in lithium microbatteries.