In this work, a multiphase microstructure consisting of nanobainte, martensite, undissolved spherical carbide, and retained blocky austenite has been prepared in an Al-alloyed high carbon steel. The effect of the amount of nanobainite on the dry sliding wear behavior of the steel is studied using a pin-on-disc tester with loads ranging from 25–75 N. The results show that, there is no significant differences in specific wear rate (SWR) for samples with various amounts of nanobainite when the normal load is 25 N. While, the SWR firstly decreases and then increases with increasing the amount of nanobainite, and the optimum wear resistance is obtained for samples with 60 vol.% nanobainite, when the applied load increases to 50 and 75 N. The improved wear resistance is attributed to the peak hardness increment resulted from the transformation of retained austenite to martensite, work hardening, along with amorphization and nanocrystallization of the worn surface. In addition, the highest toughness of the samples with 60 vol.% nanobainite is also proven to play a positive role in resisting sliding wear. EDS (energy dispersion spectrum) and XRD (X-ray diffraction) examinations reveal that the predominant failure mechanism is oxidative wear.