<P>Intracellular polymer substances (IPS) from bacterial cells were used as a novel template to synthesize porous structured polyaniline (PANI) in this study. The specific surface area of the IPS-induced PANI was ∼1.8 times that of the pristine PANI. The dosage of the bacterial cell was optimized at an optical density of 0.536. A conductivity of ∼3.1 S/cm was achieved for the IPS-induced porous PANI and was about 4 times higher than that of the PANI synthesized without templates. The improved crystallinity, decreased <I>d</I>-spacing, and lower band gap were disclosed to contribute together to the improved conductivity of the IPS-induced PANI. This porous PANI was used as a conductive medium to improve the electron transfer among anaerobic microorganisms, and thus accelerated to produce methane (CH<SUB>4</SUB>) gas from wastewater. The IPS-induced PANI with the conductivity ranging from 0.7 to 3.1 S/cm was found to have a positive influence on the production of CH<SUB>4</SUB>.</P><P>IPS released from bacterial cells is used as a novel template to synthesize porous and conductive nano-PANI for enhanced CH<SUB>4</SUB> production from wastewater.</P><BR>[FIG OMISSION]</BR>