Most studies on membrane chlorination have been investigated in an unpressurized chlorination mode, even if the polyamide membrane was continuously exposed to chlorine under high operating pressure in real water/wastewater treatment plants. In this study, performance changes due to polyamide membrane chlorination were investigated in both pressurized and unpressurized chlorination modes. Chlorination in an unpressurized mode showed a flux increase at high pH and a flux decline at low pH due to the compaction and swelling of the polyamide chains, respectively. On the other hand, chlorination performed in a pressurized mode decreased the water flux in both acidic and alkaline conditions, showing that compaction is overwhelming compared to swelling. The permeability of HOCl, a dominant species at low pH, through the polyamide membrane was pH independent and almost similar to the system recovery, but the permeability of OCl(-), which is dominant at high pH, was maxima at a neutral pH. The different performance behaviors of membranes chlorinated at various pH conditions in the presence or absence of applied pressure could be explained by the permeability of chlorine species and compaction/swelling of polymer chains after chlorination. The effect of membrane chlorination on the chemical property changes at the two different modes was confirmed using attenuated total reflection Fourier transform infrared analysis, and a conceptual model of performance change was proposed to explain the performance discrepancy between the two chlorination modes.