Higher alcohol synthesis (HAS) from syngas has attracted much attention and Cu-modified Fischer–Tropsch (FT) catalysts exhibited promising catalytic performance for HAS. In this paper, three model modified FT catalysts, CuFe, CuCo and CuNi nanoparticles, were synthesized by co-reduction method for the comparison of their performance in HAS. XRD, TEM and EDS characterizations for spent samples indicate that severe phase separation of Cu and Fe took place for CuFe, and Cu@Co core–shell structure formed with co-existence of Cu–Co alloy nanoparticles for CuCo, but only Cu–Ni alloys were observed for CuNi. Such structural change led to different performance in higher alcohol synthesis. As a result, CuFe mainly kept the original FT property of Fe, CuCo showed different performance from Co, and CuNi performed as methanol catalyst.