Persistent emission is a well-known property of cadmium metasilicate (CdSiO3) doped and co-doped with rare earth ions due to the ease of choosing the desired luminescence colour, as well as the possibility of adjusting the emission colour and the luminescence duration. Experimental work has demonstrated that combinations of different rare earth ions can produce different emission spectra colours as well as modify the lifetime of emissions. Theoretical work demonstrated a preference of single dopants to substitute cadmium sites with a Cd-vacancy as a compensation mechanism. To help elucidate the luminescent mechanisms through structural modification and consequently modification of the crystal field generated in the material by the defective region, in this work, several configurations for combined defects were tested considering the distance and preferential configuration of all the defects that comprise the system, as well as the possibility of a high concentration of these defects. Results showed a preferential arrangement for the incorporation of a Cd-vacancy as a form of charge compensation. The arrangement forms an angle closer to 180° considering the Cd-vacancy as vertex and presents a distance of around 7 Å between rare earth ions. It was also identified that the formation of a single pair with two different RE3+ ions close to a cadmium vacancy are minimally energetically more favourable to be formed in relation to clusters of dopants and co-dopants. This indicates that at low doping concentrations, RE3+ dopant pairs will form separately, but by increasing the concentration it is possible to form a cluster of defects involving RE3+. This may explain the low concentrations of dopants in this matrix. The distortion caused in the local lattice by the presence of a RE3+ pair of different dopants is bigger than the distortion caused by a RE3+ pair of dopants of the same chemical species. Therefore, CdSiO3: RE13+, RE23+ has a crystal field that is different from the crystal field experienced by RE3+ as a single dopant and the presence of the co-dopant ion will modify the luminescence of the system even though the generating defect of the luminescent centre remains the same.