Current study deals with the surface modification of acid activated carbon (prepared from Pongamia pinnata shells) with Cetyltrimethylammonium bromide (CTAB) and its role as an adsorbent in eliminating anionic azo dyes viz. Congo red (CR) and Direct blue 6 (DB) from single and binary adsorptive systems. Binary adsorptive system involved the synergistic and antagonistic influence of one dye over the adsorption of other dye. Physico-chemical alterations due to surfactant modification and post adsorption were studied using atomic force microscopy (AFM), Zeta Potential, scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), surface area analysis and Fourier-transformed infrared spectroscopy (FTIR). Process parameters influencing efficient adsorption of CR and DB species viz. initial pH of dye solution, adsorbent dosage, incubation temperature and initial concentration of dye species were optimised. Sorbate-sorbent interaction studies for single adsorptive system revealed sorbate's monolayer formation over adsorbent's surface and the involvement of chemisorption, as verified by Langmuir isotherm model and pseudo-second order model, respectively. Langmuir maximum adsorption capacity of the adsorbent was 555.56 mg/g for CR and 625.00 mg/g for DB. Meanwhile, for binary adsorptive system, competitive Langmuir model verified both CR and DB had antagonistic/competitive effect over each other's adsorption. Thermodynamic analysis revealed the adsorptive process as exothermic, spontaneous and thermodynamically favourable with an elevated degree of dis-orderedness. Co-existing cations and anions has nominal effect on the adsorption capacity of dyes. Recyclability studies verified a modest efficiency of 62.52% for CR and 50.47% for DB species after the end of 4th adsorption-desorption cycle; thus affirming its recyclability potential. Phytotoxic assay affirmed the effectivity of the adsorbent in adsorbing dye species from aqueous solutions using Vigna mungo seeds as the model.