This study aims to develop a mathematical formulation of superstructure multi-objective optimization to find optimal pathways of high-CO2 natural gas and PV-hydrogen to chemicals and fuels integrated with CO2 sequestration. A mixed-integer nonlinear programming optimization model is used to compete along 56 pathways in the superstructure optimization network. The model was developed with the general algebraic modeling system and computed with the standard branch and bound (SBB) solver to maximize annual net profit and minimize annual net CO2 emissions. The result shows the selected products in 2020 are liquefied natural gas, methanol, dimethyl ether, formic acid, and acetic acid, with annual net profits and net CO2 emissions of 38.17 million $/year and −8.47 million tons of CO2/year, respectively. In the projection analysis, the annual net profit growth results at a compounding annual growth rate of 7.85% per year between 2020 and 2060, while annual net CO2 emissions decrease until −16.37 million tons of CO2/year in 2060. In 2030, blue acetic acid will be selected via all separation processes. For 2050, the synfuel via partial membrane separation is selected. The other products, formic acid, methanol, and acetic acid via membrane separation (full and partial), will always be selected between 2020 and 2060. Therefore, this could be a future strategy for monetizing high–CO2–content natural gas sources with low-carbon process development.