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The rapidly increasing demand for sustainable energy supply coupled with the fast declining fossil fuel reserves has sparked a lot of scientific interest on energy conservation devices, however, a good number of these devices are analyzed by the energetic performance criteria based on the first law of thermodynamics only.The first law of thermodynamics fails to account for the entropy generation, the degradation of energy in a process or to give the quality of the energy in question. In this study, the useful concept of exergy utilization, is analyzed and applied to the boiler system in other to overcome the limitations of the first law of thermodynamics. The study is carried out on the boiler (101-B-01) at the Warri Refinery and Petrochemical Company which uses fuel oil as the base fuel. The energy and exergy flow and their efficiencies in the boiler subsections were determined. It was found that the combustion chamber is the major contributor of exergy destruction followed by the heat exchanger of the boiler system.