The solvatothermal reactions of V 2 O 5 , the appropriate organoamine and HF in the temperature range 100–180°C yielded a series of vanadium fluorides and oxyfluorides. The compounds [NH 4 ][H 3 N(CH 2 ) 2 NH 3 ][VF 6 ] (1) and [H 3 N(CH 2 ) 2 NH 3 ][VF 5 (H 2 O)] (2) contain mononuclear V(III) anions, while [H 3 N(CH 2 ) 2 NH 2 (CH 2 ) 2 NH 3 ] 2 [VF 5 (H 2 O)] 2 [VOF 4 (H 2 O)] (3) exhibits both V(IV) and V(III) mononuclear anions. Both compound 4, [H 3 NCH 2 (C 6 H 4 )CH 2 NH 3 ][VOF 4 ]·H 2 O (4·H 2 O) and compound 5, [HN(C 2 H 4 ) 3 NH][V 2 O 2 F 6 (H 2 O) 2 ] (5) contain binuclear anions constructed from edge-sharing V(IV) octahedra. In contrast, [H 3 N(CH 2 ) 2 NH 2 (CH 2 ) 2 NH 3 ] 2 [V 4 O 4 F 14 (H 2 O) 2 ], (6) exhibits a tetranuclear unit of edge- and corner-sharing V(IV) octahedra. Compound 7, [H 3 N(CH 2 ) 2 NH 2 ][VF 5 ], contains chains of corner-sharing {V IV F 6 } octahedra, while [H 2 N(C 2 H 4 ) 2 NH 2 ] 3 [V 4 F 17 O]·1.5H 2 O (8·1.5H 2 O) is two-dimensional with a layer of V(III) and V(IV) octahedra in an edge- and corner-sharing arrangement. In the case of [H 3 N(CH 2 ) 2 NH 3 ][V 2 O 6 ] (9), there was no fluoride incorporation, and the {V2O6}n2n- anion is a one-dimensional chain of corner-sharing V(V) tetrahedra.