Composite films based on bacterial cellulose (BC) modified with conductive polymer PEDOT/PSS are synthesized. Structural, optical and electrical properties of such composite films are investigated. It was found that the obtained BC:PEDOT/PSS films characterized by strong absorption in the red and near-infrared spectral region and by weak intensity of photoluminescence at 300K. The temperature dependence of the resistivity of the BC:PEDOT/PSS films follows a power law in the temperature interval 300–80K and the resistivity values vary weakly with time. The charge carrier transport in the BC:PEDOT/PSS composite films governed mainly by the charge transport in the conducting polymer. The obtained BC:PEDOT/PSS films are promising for application as biocompatible electrodes, temperature sensors and other biochips, which are compatible with technology of printable organic electronics.