AbstractMononuclear trivalent lanthanide complexes with formula [Ln(L)(NO3)3] [in which L=4,4‐difluoro‐8‐(2′:2′′;6′′:2′′′‐terpyridin‐4′′‐yl)‐1,3,5,7‐tetramethyl‐2,6‐diethyl‐4‐bora‐3a,4a‐diaza‐s‐indacene (Boditerpy)] are reported for Ln=Yb, Nd, Er, La and Gd. According to the crystal structure of the Yb complex, the lanthanide ion is bound to the terdentate terpyridine and the inner coordination sphere of the nine‐coordinate lanthanide ion is completed by three bidentate nitrate anions. The coordination polyhedron can be described as a distorted tricapped antiprism. The terpyridine chelate is almost planar and tilted by nearly 60° from the indacene subunit. FT‐IR spectra confirm the bidentate binding mode of the nitrate anions for the other complexes. NMR and ES‐MS spectra (through characteristic isotopic patterns) confirm the chemical formulation. The complexes have high molar absorption coefficients in the visible spectral region (65 000 M−1 cm−1 at 529 nm) and display sizeable NIR luminescence (900 to 1600 nm, for Ln=Yb, Nd and Er), upon irradiation through the electronic state of the indacene moiety at 514 nm. Crystal‐field splitting was analysed at low temperature. The quantum yield of the Yb solution (10−4 M) in dichloromethane amounts to 0.31 %, corresponding to a sensitisation efficacy of the ligand of ca. 63 %.