In this research, n-dodecane and world-average jet fuel (JW) are selected as single and multicomponent surrogate fuel of aviation kerosene to study the Jet-A spray combustion characteristics. The spray combustion phenomena are simulated using large eddy simulation coupled with detailed chemical reaction mechanism. Proper orthogonal decomposition method is applied to analyze the flow field characteristics, and the instantaneous velocity field is decomposed into four parts, namely, the mean part, coherent part, transition part, and turbulent part, respectively. The four parts have their own characteristics. In terms of different fuels, JW has a higher intensity of coherent structures and local vortices than n-dodecane, which promotes the fuel–air mixing and improves the combustion characteristics, and the soot formation is significantly reduced. In addition, with the increase of initial temperature, the combustion is more intense, the ignition delay time is advanced, the flame liftoff length is reduced, and soot formation is increased accordingly.