The current study revealed the effects of reflow temperature and the reflow time on the interfacial embrittlement of SnBi/Cu joints. When the reflow temperature is below 220 °C, the joints reflowed for 150 min often fail in brittle mode because the Bi atoms from the SnBi solder easily segregated at the Cu3Sn/Cu interface. In contrast, Bi embrittlement did not occur for joints reflowed at above 260 °C for 150 min because the Bi particles were frozen in the Cu3Sn layer during the formation of intermetallic compounds (IMC) at the initial reflow stage, mainly located at the Cu3Sn grain boundary. It is interesting to note that the Bi embrittlement did occur when the joints were reflowed at above 260 °C for 250 min, which should be attributed to Bi diffusion. It is concluded that the Bi particles are frozen in the Cu3Sn layer with increasing reflow temperature, that cannot eliminate Bi embrittlement, and can only delay the occurrence of Bi embrittlement.