During the heating process the temperature-induced liquid–liquid structure transition (LLST) of Al86Ni9La5 melt from 1320 to 1490 K was identified by both electrical resistivity and differential thermal analysis measurement. The effects of liquid structural change on the crystallization behavior and glass forming ability (GFA) of Al86Ni9La5 alloy were investigated. The amorphous samples prepared at different melt temperatures according to the liquid states were obtained. The results showed that the formation of intermetallic compounds during the crystallization process of the samples prepared below and within the LLST temperature range was earlier than that prepared above the LLST temperature range. The sample prepared above the LLST temperature range had the lowest GFA.