In the process of submarine oil exploitation and crude oil shipping, the offshore oil leakage accidents occur frequently. In the process of oil spill weathering on the sea, the oil is potentially mixed with water to form oil–water emulsification. The in situ burning is a low‐pollution and high‐efficiency method to eliminate the spilled oil. Meanwhile, as an alternative fuel, the emulsified diesel fuel has the advantage of energy saving and emission reduction. The combustion behaviors of pool fire of diesel fuel–water emulsifications are experimentally studied using three circular fuel reservoirs (10, 15, 20 cm) and five mass proportions of water (0%, 5%, 10%, 15%, 20%). The unsteady combustion process of emulsified diesel fuel is appreciated based on combustion phenomenon, mass burning rate, and flame length. The effects of pool diameter, ratio of water content, and initial fuel thickness on burning rate and flame length are revealed. The primary heat transfer mode in controlling the combustion behavior is explored according to the coupling factors of physical boundary of fuel reservoir, flame, and wall temperatures. This work is of great significance for understanding the combustion behavior of oil spill on the sea and optimizing the removal scheme of oil spill pollutants.