A theoretical protocol to study the sensitization and emission mechanism in lanthanide compounds on the basis of multireference CASSCF/PT2 calculations is proposed and applied to [Eu(NO)(dppz-CN)] and [Eu(NO)(dppz-NO)] compounds synthesized and characterized herein. The method consists of a fragmentation scheme where both the ligand and the lanthanide fragments were calculated separately but at the same level of theory, using ab initio wave-function-based methods which are adequate for the treatment of quasi-degenerate states. This is based on the fact that the absorption is ligand-localized and the emission is europium-centered. This characteristic allowed us to describe the most probable energy transfer pathways that take place in the complexes, which involved an ISC between the S to T ligand states, energy transfer to D in the lanthanide fragment, and further D → F emission. For both compounds, the triplet and D states were determined at the CASPT2 level to be around ∼26000 and ∼22400 cm, respectively. This difference is in the optimal range for the energy transfer process. Finally, the emissive state D was found at ∼18000 cm and the emission bands in the range 550-700 nm, in quite good agreement with the experimental results.