Two different groups of MgCuFe catalysts derived from hydrotalcite-like precursors were prepared through ultrasound-assisted (US) co-precipitation and solvent-free ball milling methods (BM). The catalysts were activated at 623°K, 1.5 MPa for 4 h in syngas, and their performances in the production of fuels through Fischer–Tropsch (FT) synthesis were evaluated in a fixed bed reactor at temperatures ranging from 473° to 573°K and 2 MPa and H2/CO molar ratio of 2. The physicochemical properties of the fresh and spent catalysts were investigated and characterized using different methods, including XRPD, ICP-OES, SEM, and TEM. Catalysts displayed similar catalytic activity for both BM and US with minor differences when operating at temperatures from 473° to 523°K. The results hint at the possibility of using synthetic hydrotalcites as Fe-based catalysts for the Fischer–Tropsch synthesis.