Large-scale deployment of CO2 capture, transport, and storage (CCTS) requires the rolling-out of extensive value chains. In this study, we present the development, design, techno-economic, environmental, and regulatory analysis of four pioneering chains that capture and condition CO2 from existing European industrial plants and their multi-modal transport to selected ports in Northern Europe. The pioneering chains can avoid between 65% and 87% of the industrial emissions, including scope 3, with a cost of CO2 avoided ranging between 100 and 300 euro/tCO2. The economic and environmental performance of the CCTS chains are substantially affected by the geographic location of the industrial emitters and the CO2 volumes to be transported. The analysis relies on the assumption that the four industrial plants would be early movers. While, in the future, technology maturation and infrastructure development are expected to reduce costs and emissions associated with the CCTS chain, this study quantifies and presents the current economic burden that must be overcome to initiate a needed widespread implementation of CCTS.