Abstract A variable temperature single-crystal X-ray diffraction study was undertaken on the intermetallic compound YbCuBi, which undergoes a phase transition at ∼375 K. At low temperatures (T = 193 K, a = 4.5821(3) Å, c = 7.8107(8) Å; T = 295 K, a = 4.5825(6) Å, c = 7.8597(10) Å), YbCuBi adopts the LiGaGe-type (ordered CaIn2-type) structure (Pearson symbol hP6, space group P63 mc, Z = 2). At high temperatures (T = 393 K, a = 4.5885(14) Å, c = 7.913(2) Å; T = 473 K, a = 4.594(4) Å, c = 7.928(6) Å), YbCuBi adopts the ZrBeSi-type (ordered Ni2In-type) structure (Pearson symbol hP6, space group P63/mmc, Z = 2). The structure consists of Yb atoms separating hexagonal ∞ 2[CuBi] nets, which are buckled at low temperatures but planar at high temperatures.