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Luminescent lanthanide fluoride core–shell (LaF3:Tb3+,Ce3+@SiO2‐NH2) nanoparticles, with acetylsalicylic acid (aspirin) coated on the surface have been obtained. The synthesized products, which combine the potential located in the silica shell with the luminescent activity of the core, were characterized in detail with the use of luminescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and transmission electron microscopy (TEM) methods. The in vitro effects of the modified luminescent nanoparticles on human red blood cell (RBC) membrane permeability, RBC shape, and sedimentation rate were investigated to assess the hemocompatibility of the obtained compounds. This study demonstrates that LaF3: Tb3+ 5 %, Ce3+ 10 %@SiO2‐NH2 nanoparticles with acetylsalicylic acid (aspirin) coated on the surface are very good precursors for multifunctional drug‐delivery systems or bio‐imaging probes that can be used safely in potential biomedical applications.

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