An exploratory study of the hydrothermal chemistry of vanadium in HF solutions has resulted in the preparation of four new vanadium (III) fluorides with chainlike structural motifs. [NH4](2)[VF5] (1) and [C2N2H10][VF5] (2) feature infinite chains of trans corner-sharing VF4F2/2 octahedra, [C4N2H6][VF5]center dot H2O (3) has cis corner-sharing [VF4F2/2](infinity) chains, and [C10N2H8][VF3] (4) has trans corner-sharing [VF2F2/2](infinity) chains bridged into sheets by the 4,4'-bipy linker. All four compounds exhibit antiferromagnetic behavior.