Two series of vanadyl complexes derived from bis(o-hydroxybenzoyl)methane were reported. The mesomorphic properties of the compounds 1 and 2 were studied by differential scanning calorimetry (DSC) and polarizing optical microscopy. Formation of the columnar mesophases was found to be dependent on the sidechain density around the mesogenic core. All the compounds 2 with six alkoxy sidechains exhibited columnar hexagonal (Col_h) phases, however, compounds 1 with two alkoxy sidechains formed crystalline phases. Studies of variable-temperature IR spectra for compounds 2 indicated that linear polymeric structures were observed both in the mesophase and crystalline phase. The crystal and molecular structure of 1 (n = 8) were determined by means of X-ray single crystal analysis. It crystallizes in the monoclinic space group P2₁/c, with a = 14.6581 (1) Å, b = 14.5933 (2) Å, c = 21.7985 (1) Å, α = 90°, β = 100.320 (1)°, γ = 90°, and Z = 4. The vanadyl center is bonded in a typical five-coordinate fashion with a solvated tetrahydrofuran molecule sixth-coordinated opposite the axial oxygen. The EPR spectra measured at variable temperatures were also studied.