In this work, we compiled our research on lanthanide-based luminescent materials, prepared down-shifter layers, and studied their effect on photovoltaic (PV) mini-modules. The compounds we have prepared (C1-C17), with formulas [Eu2(phen)2(bz)6] (C1), [Eu2(bphen)2(bz)6] (C2), [Eu(tta)3bphen] (C3), [Eu(bta)3pyz-phen] (C4), [Eu(tta)3pyz-phen] (C5), [Eu(bta)3me-phen] (C6), [Er(bta)3me-phen] (C7), [Yb(bta)3me-phen] (C8), [Gd(bta)3me-phen] (C9), [Yb(bta)3pyz-phen] (C10), [Er(tta)3pyz-phen] (C11), [Eu2(bz)4(tta)2(phen)2] (C12), [Gd2(bz)4(tta)2(phen)2] (C13), [EuTb(bz)4(tta)2(phen)2] (C14), [EuGd(bz)4(tta)2(phen)2] (C15), [Eu1.2Gd0.8(bz)4(tta)2(phen)2] (C16) and [Eu1.6Gd0.4(bz)4(tta)2(phen)2] (C17), can be grouped into three families based on their composition: Series C1–6 were synthesized using Eu3+ ions and phenanthroline derivatives as the neutral ligands, and fluorinated β-diketonates as the anionic ligands. Complexes C7–11 were prepared with ligands similar to those of compounds C1–6 but were synthesized with Er3+, Yb3+, or Gd3+ ions. Series C12–17 exhibit the general formula [M1M2(bz)4(tta)2(phen)2], where M1 and M2 can be Eu3+, Gd3+, or Tb3+ ions, and the ligands are benzoate (bz–), 2-thenoyltrifluoroacetone (tta–) and 1,10–phenanthroline (phen). All compounds were characterized using X-ray techniques, and their photoluminescent properties were studied. We then examined their impact on the EQE (External Quantum Efficiency) of PV mini-modules and their durability in a climate chamber when embedded in PMMA and EVA films. This review emphasizes the methodology employed and the key findings, including enhanced mini-module efficiency. Additionally, we present promising results on the application of compound C6 in a bifacial solar cell.