Doping active agents into metal-organic frameworks (MOFs) is widely sought after owing to its potential to enhance adsorption and photocatalytic efficiency, surpassing the potential of bare frameworks. This study incorporated a catalytically active NS-ligand (1,2-benzisothiazolin-3-one) into a very stable and porous PCN-600 MOF via an in situ synthesis approach. The NS-ligand, which matched with the host ligands of PCN-600, enabled the highly efficient synthesis of NS-co-doped MOFs. The pristine PCN-600 framework and morphology were retained in the MOF altered with the NS-ligand, as demonstrated by XRD, FTIR, and SEM characterizations. A high electron density was generated due to the synergistic effect between the defects in the NS-co-doped photocatalyst and engineered active sites. This facilitated the adsorption-assisted photocatalytic decontamination of metronidazole with an 87% removal by PCN-600-NS-10 compared to 43% by pristine PCN-600 within a total time of 150 min. The MOF doped with the NS-ligand exhibited a reduced band gap and enhanced adsorption and photocatalytic capabilities compared to pristine PCN-600. The impact of operational parameters, such as catalyst dosage, initial solution pH, and MNZ concentration, was also explored. Pseudo-second and pseudo-first order models were found to describe the adsorption and degradation kinetics of metronidazole and the Dubinin-Radushkevich model was found to fit the equilibrium adsorption results. The thermodynamic characteristics of adsorption processes (Delta G(ads), Delta H-ads, and Delta S-ads) demonstrated that adsorption was physical, spontaneous, and exothermic and resulted in increased entropy.