This study was to examine the bioremediation of wastewater containing a binary mixture of methyl orange (MO) and reactive black 5 (RB5), as well as bioelectricity generation in single chamber up-flow membrane-less microbial fuel cell (UFML-MFC). Decolourisation performance and power density of MFC were studied with different concentrations of binary dye (25, 50 and 75 mg/L) as influent. The colour removals evaluated from the standard curve of dye against optical density at its maximum absorption wavelength were 80.40%, 70.33% and 56.99%, respectively in the three phases of study. The decolourisation extent of RB5 is comparatively higher than MO in the binary mixture, due to the presence of more sulphonate groups in the molecular geometry of RB5. The reductive cleavage of azo bond was denoted by UV spectroscopic analysis.