There are only limited reports on vanadium(iv) oxyfluorides (VOFs) with extended crystal structures. Here we expand and enrich the list of existing VOFs with a series of 14 new materials " (n = 1-14)" prepared using ionothermal and solvothermal synthesis methods. All of these materials arise from the condensation of a dimeric structural motif. These VOFs can be classified into three groups depending on their key structural features; layer structures: "[HN2C7H6][V2O2F5]", "[HN2C4H4][V2O2F5]", "[HN2C3H4][V2O2F5]" and "V2(N2C4H4)O2F4", ladder like structures: "[NH4(HN2C3H4)][V2O2F6]", "[K(HN2C3H4)][V2O2F6]", "[HNH2CH2CH3][VOF3]", "[HN2C7H6][VOF3]", "[H2N2C4H6][V2O2F6]", "β-RbVOF3", α-KVOF3", "β-KVOF3", "[H2(NH2)2(CH2)2][V2O2F6]", and a chain structure: "[H2N2C6H12][V2O2F7]". The crystal structures of are presented, and their synthetic and structural relationships are discussed.