The aim of this manuscript is to synthesize and characterize novel silylated Sm3+ and Eu3+ complexes and incorporate them into mesoporous silica nanoparticles (MSNs) and dense silica nanoparticles (DSNs). Sm3+ and Eu3+ ion complexes were chosen for their strong UV-visible emission, deep-red luminescence, and effective interaction with bidentate organic ligands, such as 2-thenoyltrifluoroacetone (tta) and 1,10-phenanthroline (phen). Silylated ligands were employed as coupling agents to form covalent bonds between the complexes and an oxide matrix via a conventional sol-gel process. This approach aims to enhance the thermal stability and photophysical properties of the resulting hybrid material compared to free complexes. The new silylated-bidentate ligand complexes, using tta and phen as organic ligands and 3-chloropropyltriethoxysilane as the silylating agent, were characterized by FTIR, luminescence spectroscopy, and luminescence decay. After incorporation into silica nanoparticles, the hybrid materials were characterized by SEM, TEM, DLS, zeta potential, SAXS, porosity, surface area measurements, luminescence spectroscopy, and MTT assay. The results confirm the successful synthesis of new luminescent silylated complexes with high luminescence intensity and their incorporation into silica nanoparticles.