The effect of Fe addition on the structure, mechanical and wear properties of Zr–Cu–Ni–Al bulk metallic glasses (BMGs) was systematically investigated by thermal analysis, transmission electron microscopy (TEM), the compression test, the pin-on-disk macroscopic wear test and the microscopic nanoscratch test. TEM observation revealed the formation of a second glassy phase with a few nanometers in diameter in the Zr 63.6- x Cu 18 Ni 10.4 Al 8 Fe x (x = 1, 3, 5) BMGs. The results of the mechanical tests showed that although compression strength and hardness do not change much, a remarkable enhancement in plasticity occurs in the Zr 58.6 Cu 18 Ni 10.4 Al 8 Fe 5 BMG, which is presumably due to the restriction of the nano-scale second phase on shear banding. Phase separation was also found to promote multiple shear bands, enhanced toughness and oxidative wear, which work synergistically during the tribological test to improve the wear resistance of Zr–Cu–Ni–Al BMGs. These findings provide some insights into the wear mechanisms of dual-phase BMGs, which may offer new strategies for design and optimization of BMGs with desired wear performance. • Macroscopic and nano-wear characterizations are exploited to explore the tribological behavior of BMGs. • Minor Fe substitution for Zr leads to the formation of second glassy phase. • Phase separation can have a dramatic effect on the wear resistance. [ABSTRACT FROM AUTHOR]