In the present study, a synergistic effect between cationic methylene blue (MB) and anionic acid red 1 (AR1) on their concurrent adsorptive removal from aqueous binary solution onto durian rind (DR) was systematically investigated in batch mode across different parameters. The concurrent adsorption was pseudo-second-order kinetics and followed the Langmuir isotherm model, similar to their respective single component. The kinetics and intraparticle diffusion analyses demonstrated that the adsorption rate of MB was a 15-fold faster than AR1, and mass transports were governed by a combination of intraparticle and film diffusion. The synergistic effect was evidenced by an enhanced adsorption efficiency of AR1 from 27 to 42%, while that of MB was almost unchanged (97–98%). By changing the molar ratios of MB and AR1, it was found that the maximum adsorption capacity of MB and AR1 was 249 and 200 mg g−1, respectively, in the binary system higher compared with those in their respective single system (108 and 16 mg g−1). Overall data indicated that the synergistic effect was due to electrostatic interactions between cationic and anionic synthetic dyes, supported by negatively charged DR surface, leading to the formation of their stacking layers on the adsorbent surface. Novelty statement: A synergistic effect in concurrent adsorptive removal of synthetic dyes from multicomponent wastewater remains a critical research challenge. We believed that electrostatic interaction between ionic dyes could be explored to enhance their removal efficiency. This report is the first time that such a synergistic effect between cationic methylene blue (MB) and anionic acid red 1 (AR1) on their concurrent adsorption from aqueous binary system is systematically investigated. The kinetics, isotherm, thermodynamics, and mechanism of the concurrent adsorption of MB and AR1 attributed to the synergistic effect are elucidated in detail.