This study investigates the engine performance and exhaust emission of the dual-fuel operation on a single cylinder compression ignition engine from the energetic, exergetic, and sustainability points of view using experimental values. Hydrogen with different concentrations is used as fuel with diesel as the main fuel. Comparative results of the dual-fuel operation with conventional diesel fuel through experimental results demonstrated its benefits for the engine performance. The engine specific fuel consumption shows improvement and dual-fuel operation is able to achieve a better performance under most operating conditions. The emission levels of oxides of nitrogen (NOx) show a slight increase using dual fuel due to the increase in the temperature. For the speeds of 1000 and 1400 rpm with a power range from 0.74 to 3.1 kW under variable composition hydrogen/diesel mixtures, the minimum and maximum values for energy (thermal) are found to be 8.0 and 20.1%, while those for the corresponding exergy are calculated to be 7.6 and 18.8%, respectively.