In this study, zero-valent iron-copper (Fe-Cu) and iron-nickel (Fe-Ni) bimetals were prepared by disc milling for the dehalogenation of trichloroethylene vapors. For both Fe-Ni and Fe-Cu, three combinations in terms of percentage of secondary metal added were produced (1%, 5%, 20% by weight) and the formation of the bimetallic phase by milling was evaluated by X-ray diffraction (XRD) analysis. The disc milled bimetals were characterized by a homogenous distribution of Ni or Cu in the Fe phase and micrometric size visible from scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) analysis and by a relatively low specific surface area (0.2–0.7 m2/g) quantified by the Brunauer–Emmett–Teller (BET) method. The reactivity of the produced bimetals was evaluated by batch degradation tests of TCE in the gas phase with 1 day of reaction time. Fe-Ni bimetals have shown better performance in terms of TCE removal (57–75%) than Fe-Cu bimetals (41–55%). The similar specific surface area values found for the produced bimetals indicated that the enhancement in the dehalogenation achieved using bimetals is closely related to the induced catalysis. The obtained results suggest that ZVI-based bimetals produced by disc milling are effective in the dehalogenation of TCE vapors in partially saturated conditions.