In recent years, the concern from the global climate change has driven an urgent need to develop clean energy technologies that do not involve combustion process that emit carbon into the atmosphere. A promising concept is microbial fuel cells that utilize bacteria as electron donors in a bio-electrochemical cell performing a direct electron transfer via conductive protein complexes or by secretion of redox active metabolites such as quinone or phenazine derivatives. In the case of photosynthetic bacteria (cyanobacteria) electrons can also be extracted from the photosynthetic pathway mediated mostly by NADH and NADPH. In this work, we show for the first time that the intact non-photosynthetic bacteria Escherichia coli can produce photocurrent that is enhanced upon addition of an exogenous electron mediator. Furthermore, we apply 2D-fluorescence measurement to show that NADH is released from the bacterial cells, which may apply as a native electron mediator in microbial fuel cells.