The dynamic evolutionary law and tribological behavior of tribopair AISI 52100-AISI 1045 were studied via the multifractal method. Friction experiment was performed on a ring-on-disk tribometer under lubrication, and the multifractal detrended fluctuation analysis (MF-DFA) method was adapted to characterize the multifractality of the friction coefficient. The multifractal spectra first exhibited a left-hook, then right-hook, and left-hook, respectively, during the friction stages. The multifractal spectrum width W decreases in running-in friction process, maintains at small values in steady friction process, and increases rapidly in increasing friction process. Corresponding shuffled series was analyzed to distinguish that the multifractality of friction coefficient is due to the long-range correlation of the fluctuations. The results inform quantitative interpretations of friction system's tribological behavior and friction process identification.