Stabilizing global climate change to within 1.5 °C requires a reduction in greenhouse gas emissions, with a primary focus on carbon dioxide (CO₂) emissions. CO₂ flooding in oilfields has recently been recognized as an important way to reduce CO₂ emissions by storing CO₂ in oil reservoirs. This work proposes an advanced CO₂ enhanced oil recovery (EOR) method—namely, storage-driven CO₂ EOR—whose main target is to realize net-zero or even negative CO₂ emissions by sequestrating the maximum possible amount of CO₂ in oil reservoirs while accomplishing the maximum possible oil recovery. Here, dimethyl ether (DME) is employed as an efficient agent in assisting conventional CO₂ EOR for oil recovery while enhancing CO₂ sequestration in reservoirs. The results show that DME improves the solubility of CO₂ in in situ oil, which is beneficial for the solubility trapping of CO₂ storage; furthermore, the presence of DME inhibits the 'escape' of lighter hydrocarbons from crude oil due to the CO₂ extraction effect, which is critical for sustainable oil recovery. Storage-driven CO₂ EOR is superior to conventional CO₂ EOR in improving sweeping efficiency, especially during the late oil production period. This work demonstrates that storage-driven CO₂ EOR exhibits higher oil-in-place (OIP) recovery than conventional CO₂ EOR. Moreover, the amount of sequestrated CO2 in storage-driven CO₂ EOR exceeds the amount of emissions from burning the produced oil; that is, the sequestrated CO₂ offsets not only current emissions but also past CO₂ emissions. By altering developing scenarios, such as water alternating storage-driven CO₂ EOR, more CO₂ sequestration and higher oil recovery can be achieved. This work demonstrates the potential utilization of DME as an efficient additive to CO₂ for enhancing oil recovery while improving CO₂ storage in oil reservoirs.