A chiral Eu(III) coordination polymer with phase-transition behavior, [Eu(+tfc)3(m-dpeb)]n, (+tfc: (+)-3-trifluoroacetylcamphorato, m-dpeb: 1,3-bis(diphenylphosphorylethynyl)benzene) was reported for understanding the effect of polymer chain arrangement (orientation effect) on the circularly polarized luminescence (CPL) in a solid system. The phase-transition behavior of the transformable Eu(III) coordination polymer was characterized using differential scanning calorimetry and powder X-ray diffraction. The Eu(III) coordination polymer exhibited phase transition at approximately 180 °C. The magnitude of the CPL intensity was drastically changed because of the phase transition, without coordination geometrical change around the Eu(III) ion. In this study, the orientation effect of a chiral Eu(III) coordination polymer on the CPL properties in crystalline solid is demonstrated.