In the present study, the potential of Pseudomonas citronellolis 620C strain was evaluated, for the first time, to generate electricity in a standard, double chamber microbial fuel cell (MFC), with oily wastewater (OW) being the fuel at 43.625 mg/L initial chemical oxygen demand (COD). Both electrochemical and physicochemical results suggested that this P. citronellolis strain utilized efficiently the OW substrate and generated electricity in the MFC setup reaching 0.05 mW/m2 maximum power. COD removal was remarkable reaching 83.6 ± 0.1%, while qualitative and quantitative gas chromatography/mass spectrometry (GC/MS) analysis of the OW total petroleum and polycyclic aromatic hydrocarbons, and fatty acids revealed high degradation capacity. It was also determined that P. citronellolis 620C produced pyocyanin as electron shuttle in the anodic MFC chamber. To the authors’ best knowledge, this is the first study showing (phenazine-based) pyocyanin production from a species other than P. aeruginosa and, also, the first time that P. citronellolis 620C has been shown to produce electricity in a MFC. The production of pyocyanin, in combination with the formation of biofilm in the MFC anode, as observed with scanning electron microscopy (SEM) analysis, makes this P. citronellolis strain an attractive and promising candidate for wider MFC applications.