The rising demand for fossil fuels is rapidly depleting the limited sources of crude oil, leading to harmful emissions upon combustion. Consequently, developing sustainable and environment-friendly alternatives to fossil fuels has become imperative to reduce dependence on them and decrease harmful emissions. In this study, the performance of different blends prepared by mixing biofuels with super-premium gasoline (SPG) in a spark-ignition (SI) engine at different speeds is investigated through energy and exergy analysis. Three biofuels, namely ethanol, anisole, and isobutyl acetate, are considered, and these biofuels are blended with the base SPG in volumes ranging from 10% to 30%. Letters G, E, A, and IBA are used to denote SPG, ethanol, anisole, and isobutyl acetate, respectively. Experiments were conducted on a three-cylinder, four-stroke SI engine with varying speeds. The results of different anisole-SPG and isobutyl acetate-SPG blends are compared with SPG and ethanol-SPG blends. The results of the energy and exergy analysis reveal that the maximum brake thermal efficiency (BTE) and exergy efficiency are achieved when the engine runs at 2500 rpm for SPG and different blends. Furthermore, the engine emissions of carbon monoxide (CO) are found to be lowest at this engine speed. It is also investigated that the maximum BTE and exergy efficiency are obtained for AG10 and IBAG10 blends. The maximum BTE of AG10 and IBAG10 are 31.23% and 30.82%, respectively, while the maximum exergy efficiency of AG10 and IBAG10 are 24.37% and 23.82%. At 2500 rpm, the blends AG10 and IBAG10 showed a slight reduction in BTE by 1.72% and 3.02%, respectively, compared to SPG. At the same time, the exergy efficiency of the AG10 and IBAG10 blends is reduced by 1.5% and 3.72%, respectively. On the other hand, the IBAG30 blend showed 7% lower emissions of CO and NOx compared to SPG. Among all the blends, EG30 showed the lowest reduction of HC emissions by 14% compared to SPG. Additionally, the sustainability index values decreased by 0.47% and 1.19% for AG10 and IBAG10, respectively, compared to SPG at 2500 rpm.