Reactions between AF (A = Li, Na, K, Rb, Cs) and TiF (with starting n(AF):n(TiF) molar ratios in the range from 3:1 to 1:3) in anhydrous hydrogen fluoride yield [TiF], [TiF], [TiF], [TiF], and [TiF] salts. With the exception of the ATiF compounds, which consist of A cations and octahedral [TiF] anions, all of these materials arise from the condensation of TiF units. The anionic part in the crystal structures of A[TiF] (A = K, Cs) and A[TiF]·HF (A = Na, K, Rb) is composed of infinite ([TiF]) chains built of TiF octahedra sharing joint vertices. Each structure shows a slightly different geometry of the ([TiF]) chains. The crystal structure of Na[TiF]·HF is constructed from polymeric ([TiF]) anions that appear as two parallel infinite zigzag chains comprising TiF units, where each TiF unit of one chain is connected to a TiF unit of the other chain through a shared fluorine vertex. Slow decomposition of single crystals of K[TiF]·8HF and Rb[TiF]·6HF ( Shlyapnikov , I. M. ; et al. Chem. Commun. 2013 , 49 , 2703 ) leads to the formation of [TiF] (Rb) and [TiF] (K, Rb) salts. The former displays the same ([TiF]) double chain as in Na[TiF]·HF, while the anionic part in the latter, ([TiF]), represents the first example of a three-dimensional network built of TiF octahedra. The ([TiF]) anion was also found in [HO][TiF]. The crystal structure determination of Cs[TiF] revealed a new type of polymeric fluoridotitanate(IV) anion, ([TiF]). Similar to the ([TiF]) anion, it is also built of zigzag double chains comprising TiF units. However, in the former there are fewer connections between TiF units of two neighboring chains than in the latter.