The tribological behavior of an Fe-based bulk amorphous alloy while sliding against a AISI 304 disc is investigated using a unidirectional pin-on-disc type tribometer in dry and distilled water environments. The rod-shaped bulk pins are fabricated by suction casting. The crystallinities of the bulk amorphous alloys before and after the friction tests are determined by X-ray diffraction. The friction coefficient and specific wear rate of the amorphous pin in the water environment are found to be twice and thrice as much as in the dry environment at a low applied pressure, respectively. However, at a higher pressure, the friction coefficient and specific wear rate are 0.4 and 1.02 mg/(Nm/s), respectively, in the water environment. A microstructure analysis shows that the worn surface of the alloy is characterized by delamination from the smooth friction surface, and thus delamination is the main wear mechanism during the friction test in dry sliding environment. In contrast, brittle fracture morphologies are apparent on the friction surface formed in distilled water environment. For the sample tested at a lower sliding speed, the XPS data from the oxide layer are similar to those of the pure element with weak suboxide peaks. For higher sliding speeds, all the main sharp peaks representing the core level binding energies are shifted to the oxide region.