Among identified conventional fuels, liquid fossil fuels are depleting at a faster rate with an imbalance effect on atmospheric contents. It is a worldwide approach to come with an option to tackle this problem. Biodiesel and higher alcoholic compounds are projecting as the most substituting fuels generally explored because of their accessibility, easiness in synthesis, and good impact on nature. The cost and contamination issues can be rectified with the effective usage of biodiesel. Alternative fuel for diesel engines needs to satisfy all such standards fulfilled by diesel fuel. The present work provides the method of synthesizing biodiesel by transesterification and the impact of solvent in esterified oils in terms of property check. Based on likely suitability, the sample has been tested in a twin-cylinder 4-S CI engine. The effect of Pongamia methyl ester-Gasoline blend [PME-5 G] on engine performance, combustion, and emission has been analyzed for 0%, 20%, 40%, 60%, 80%, and 100% loading. It has been observed that a 5% Gasoline in Pongamia methyl ester exhibits very closer results while comparing with the diesel, parameters such as brake power of engine show 2.5 kW, 5 kW, 7.5 kW, 9.5 kW, and 12 kW at engine load of 20%, 40%, 60%, 80%, and 100%, respectively. Similarly, brake thermal efficiency at engine load of 40%, 60%, and 80% shows improvement of 8%, 6%, and 5%, respectively. The distinguished fuel properties of PME-5 G were well within the permissible levels of standards as set by the majority of countries. Hence, Pongamia methyl ester-Gasoline blend [PME-5 G] can be used in existing diesel engines without compromising the engine performance and emissions.