In this work, the tribological behaviors of the bulk AlMgB14 (BAM) were investigated under different counterface materials in deionized water. As the results show, the tribological behaviors of BAM are closely related to the counterface materials. When 316 L ball is used as the slider, the contact pair exhibits no self-lubricity proved by the higher friction coefficient (COF), about 0.33, and the adhesive wear prevails. While when Si3N4 and Al2O3 balls are used as the sliders, the contact pairs shows better self-lubricity with a COF as low as 0.03, due to the tribo-chemistry products—hydrated SiO2 and Al(OH)3 gel, respectively. In addition, BAM/Al2O3 tribo-pair presents the polishing wear, indicating a more significant self-lubricity compared with that of BAM/Si3N4 tribopair.