Wastewater treatment coupled with electricity recovery in microbial fuel cell (MFC) prefer mixed anaerobic sludge as inoculum in anodic chamber than pure stain of electroactive bacteria (EAB), due to robustness and syntrophic association. Genetic modification is difficult to adopt for mixed sludge microbes for enhancing power production of MFC. Hence, we demonstrated use of eco-friendly plant secondary metabolites (PSM) with sub-lethal concentrations to enhance the rate of extracellular electron transfer between EAB and anode and validated it in both bench-scale as well as pilot-scale MFCs. The PSMs contain tannin, saponin and essential oils, which are having electron shuttling properties and their addition to microbes can cause alteration in cell morphology, electroactive behaviour and shifting in microbial population dynamics depending upon concentrations and types of PSM used. Improvement of 2.1-times and 3.8-times in power densities was observed in two different MFCs inoculated with Eucalyptus-extract pre-treated mixed anaerobic sludge and pure culture of Pseudomonas aeruginosa, respectively, as compared to respective control MFCs operated without adding Eucalyptus-extract to inoculum. When Eucalyptus-extract-dose was spiked to anodic chamber (125 l) of pilot-scale MFC, treating septage, the current production was dramatically improved. Thus, PSM-dosing to inoculum holds exciting promise for increasing electricity production of field-scale MFCs.