This paper describes the syntheses and full characterization of perfluorinated 1H-indazoles 2-5 and hydrotris(indazolyl)borate thallium complexes 6-9 that contain linear perfluoroalkyl chains varying from two to six carbon atoms in the 3-position. In the solid state, the perfluorinated 1H-indazoles exhibit supramolecular structures that depend on the length of the perfluoroalkyl chain. A catemer of order 3 is observed for the CF2CF3 derivative 2 (chiral space group P32), catemers of order 2 are observed for the C3F7 and C4F9 derivatives 3 (chiral space group P212121, one type of helix in the unit cell) and 4 (space group P21/n, two types of helices in the unit cell), respectively, and stacks of dimers are observed for the indazole with the longer C6F13 chain 5 (space group P21/c). The perfluorinated hydrotris(indazolyl)borate thallium complexes 6-9 [TlFn-Tp4Bo,3Rf] have been obtained by a new reaction based on the reaction of HBBr2 (generated in situ from BBr3 and Et3SiH) with the indazolates of 2-5 followed by cation exchange. The X-ray crystal structure of [TlF33-Tp4Bo,3C3F7] 7 shows that, in addition to coordination to the three nitrogens, the thallium is buried in a nest of fluorines with seven short intramolecular TlF contacts with the pendant perfluoropropyl chains. The potential of these highly fluorinated molecules to act as ligands is highlighted.