Abstract In this study, for the first time, a selenium-doped mesoporous biochar was prepared and efficiently employed for sodium diclofenac and reactive orange 16 dye adsorption. The characterization results indicated that selenium doping had a remarkable impact on Biochar-Se morphological and physicochemical structures. The efficacy of developed biochar samples on reactive orange 16 (RO-16) and diclofenac (DCF) removals was fully investigated. For both molecules (DCF and RO-16), Liu’s equilibrium model offered the best fitness with maximum adsorption capacity values of 355 mg g−1 for DCF and 538 mg g−1 for RO-16 for Biochar-Se. Multiple mechanisms including pore filling, π-π interaction, and hydrogen bonding between the Biochar-Se and DCF/RO-16 molecules were involved in the adsorption process. Se-nanoparticles formed metal–oxygen bonds, which boosted the adsorption of DCF and RO-16 molecules. The current work offered a feasible approach for the development of Se-doped biochar adsorbent that is incredibly effective in treating wastewater.