A bis(β‐diketone), 1,3‐bis(4,4,4‐trifluoro‐1,3‐dioxobutyl)phenyl (BTP), which contains a trifluorinated alkyl group, has been exploited to obtain three series of visible‐light sensitive dinuclear rare‐earth complexes with the general formula [Ln2(BTP)3L2] [Ln = Nd, L = DME (1), bpy (2), and phen (3); Ln = Yb, L = DME (4), bpy (5), and phen (6); Ln = Er, L = DME (7); DME = ethylene glycol dimethyl ether, bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline]. An X‐ray crystallographic analysis revealed that complexes 1, 2, 4, 5, and 7 are triple‐stranded helical dinuclear structures that are formed by three bis(bidentate) ligands with two lanthanide ions. The room‐temperature near‐IR luminescent properties of complexes 1–6 show that this bis(β‐diketone) can effectively sensitize rare earths (Nd3+, Yb3+) and produce typical near‐infrared luminescence upon excitation with visible light of the corresponding Nd3+ and Yb3+ ions. Additionally, two bidentate nitrogen ancillary ligands, 2,2‐bipydine (bpy) and 1,10‐phenanthroline (phen), have been applied to enhance the NIR luminescent properties.