In order to investigate the effect of Cr content on the microstructures and oxidation wear properties of high-boron high-speed steel (HBHSS), so as to explore oxidation wear resistant materials (e.g., hot rollers), a scanning electron microscope, an X-ray diffractometer, an electron probe X-ray microanalysis and an oxidation wear test at elevated temperatures were employed to investigate worn surfaces and worn layers. The results showed that the addition of Cr resulted in the transformation of martensite into ferrite and pearlite, while the size of the grid morphology of borides in HBHSSs was refined. After oxidation wear, oxide scales were formed and the high-temperature oxidation wear resistance of HBHSSs was gradually improved with increased additions of Cr. Meanwhile, an interaction between temperature and load in HBHSSs during oxidation wear occurred, and the temperature had more influence on the oxidation wear properties of HBHSSs. SEM observations indicated that a uniform and compact oxide film of HBHSSs in the worn surface at elevated temperatures was generated on the worn surface, and the addition of Cr also reduced the thickness of oxides and inhibited the spallation of worn layers, which was attributed to improvements in microhardness and oxidation resistance of the matrix in HBHSSs. A synergistic effect of temperature and load in HBHSSs with various Cr additions may dominate the oxidation wear process and the formation and spallation of oxide films.