Dissolution of LiCl or LiPF₆ in pyridine or vinyl­pyridine and slow vapor diffusion of this solution with diethyl ether gives solvates of the lithium salts coordinated by pyridine ligands. In the case of the hexa­fluorophosphate salts, the chemical species formed are similar, namely binary salts with hexa­fluoro­phosphate counter-ions. In contrast, the solvates with LiCl are structurally dissimilar, with one forming a one-dimensional ionic polymer of fused LiCl rhombs and the other crystallizing as an isolated mol­ecular unit with a complex array of van der Waals inter­actions of neighboring mol­ecules.