The present study aims to gain insight into the circularly polarised luminescence (CPL) of lanthanide complexes through the angle of one of their elements, namely Samarium. The simulation of luminescent properties of Samarium(iii) complexes remains a challenge for computational chemistry, considering the multiconfigurational character of the electronic structure, the importance of the spin-orbit coupling and the fact that its emissive level is high in energy and preceded by numerous states of various multiplicity. Herein, a methodology based on CASSCF/RASSI-SO calculations is exposed and applied to simulate the CPL properties of two different Samarium(iii) complexes, presenting either a rigid or a flexible architecture around the centre ion.