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This paper explores the potential for reducing transport-related greenhouse gas (GHG) emissions by introducing high-efficiency spark-ignition engines with a dual-fuel injection system to customize the octane of the fuels based on real-time engine requirements. It is assumed that a vehicle was equipped with two fuel tanks and two injection systems; one port fuel injection and one direct injection line separately. Each tank carried low octane and high octane fuel so that real-time octane blending was occurred in the combustion chamber when needed (Octane On-Demand: OOD). A refinery naphtha was selected for low octane fuel (RON=61), because of its similarity to gasoline properties but a less processed, easier to produce without changing a refinery configuration. Three oxygenates were used for high octane knock-resistant fuels in a direct injection line: methanol, MTBE, and ETBE.