Bismuth and its alloys are candidates for Pb-free high-temperature solders that can be substituted for conventional Pb-rich Pb−Sn solders (melting point (mp) = 573 – 583 K). However, inferior properties such as brittleness and weak bonding strength should be improved for practical use. To that end, BiCu−X (X=Sb, Sn, and Zn) Pb-free high-temperature solders are proposed. Miscibility gaps in liquid BiCu−X alloys were surveyed using the thermodynamic database ADAMIS (alloy database for micro-solders), and compositions of the BiCu−X solders were designed on the basis of calculation. In-situ composite solders that consist of a Bi-base matrix with fine intermetallic compound (IMC) particles were produced by gas-atomizing and melt-spinning methods. The interfacial reaction between in-situ composite solders and Cu or Ni substrates was investigated. The IMCs at the interface formed a thin, uniform layer, which is an appropriate morphology for a reliable solder joint.