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• A bottom-up estimation of CO 2 mitigation potential of combined options for a case-study refinery. • A dynamic CO 2 mitigation potential over time is based on measure interactions for each pathway. • Co-processing account for 60% of the portfolio followed by CCS with 23%, GE with 7%, and H 2 with 6% • The oil and gas industry could reach carbon neutral operation at factory gate. • The methodological approach brings insights to define optimal transition routes of the industry. The oil and gas industry is responsible for 6% of total global CO 2 emissions, from exploration to downstream petrochemical production and account for another 50% when including the use of its products. Thus, this industry has a significant role in realising the target of net "zero" CO 2 emissions by 2070, essential to limit global warming to 1.8 °C [2], as introduced under the Paris agreement. Currently, the interactions of an extensive set of individual and combined CO 2 mitigation measures along the value chain and over time are poorly assessed. This paper aims to assess a bottom-up CO 2 mitigation potential for a complex refinery, including portfolios of combined mitigation options, considering synergies, overlap, and interactions over time for more realistic insight into the costs and constraints of the mitigation portfolio. A total of 40 measures were identified, covering a wide range of technologies such as energy efficiency measures (EEM), carbon capture and storage (CCS), bio-oil co-processing, blue and green hydrogen (BH 2 , GH 2), green electricity import, and electrification of refining processes linked to the transition of the Colombian energy systems. Five deployment pathways were assessed to achieve different specific targets: 1-base case scenario, 2-less effort, 3-maximum CO 2 avoidance, 4-INDC, and 5-measures below 200 €/t CO 2. Two scenarios (3 and 5) gave the highest GHG emission reduction potentials of 106% and 98% of refining process emissions, respectively. Although significant, it represent only around 13% of the life-cycle emissions when including upstream and final-use emissions of the produced fuels. Bio-oil co-processing options account for around 60% of the mitigation options portfolio, followed by CCS (23%), green electricity (7%) and green H 2 (6%). The devised methodological approach in this study can also be applied to assess other energy-intensive industrial complexes and shed light on the bias for estimating CO 2 mitigation potentials, especially when combining different mitigation options. This is turn is vital to define optimal transition pathways of industrial complexes. [ABSTRACT FROM AUTHOR]