To fend off the probable adverse effects of climate change as well as the subsequent economic and social impacts as a consequence of humans’ industrial activities, drastic changes are required in the way of processing, managing and exploiting natural resources. Based on a case study, the present report combines life-cycle assessment and life-cycle costing techniques on the basis of environmental externalities monetization with a view to conducting a multi-perspective comparative assessment of different chlorine manufacturing systems so that to identify which alternative can lead to the lowest environmental footprint and cost-intensity. Our findings suggest that the most cost-effective and less environmentally-intensive technical solution concerns the modification of the electrolysis cell’s configuration type from gap to zero-gap one when the heat is supplied by an on-site CHP facility. This modification is accompanied by 39% reduction of CO2 emissions in the membrane electrolysis stage and 24% reduction in the total CO2 emissions per ton of chlorine produced. Moreover, annual savings and profits increase while chain-related environmental costs substantially decline.