Silica nanoparticles of 12 nm diameter were surface-doped with ca. 350 (TTF-dppz)­Yb­(III) surface species, containing bis­(propylthio)­tetrathiafulvenyl­i­dipyrido-3,2-a:2′,3-c­phenazine (TTF-dppz) as an antenna ligand through a surface organometallic chemistry approach. These nanoparticles absorb and emit in the NIR (λabs = 750 nm, λem = 983 and 1050 nm) with a lifetime (τ1) of 2.8 μs, similarly to the corresponding Yb­(III) molecular complex (λabs = 750 nm, λem = 975, 986, 1009, and 1020 nm with τ1 = 6.93 μs). The silica materials were fully characterized using combined spectroscopic techniques (IR, NMR, UV–vis, luminescence and lifetime), molecular models and isostructural diamagnetic yttrium-containing materials for easier characterization by NMR spectroscopy. Having established the surface structures and photophysical properties of these nanoparticles, we transposed this methodology to larger silica particles with a diameter of ca. 100 nm. These larger nanoparticles have similar photophysical properties and contain ca. 30 000 chromophores, making possible one-photon NIR-to-NIR emission optical microscopy imaging of single nanoparticles.