The crystal structure of the promising Li-ion battery cathode material LiFeBO3 has been redetermined based on the results of single crystal X-ray diffraction data. A commensurate modulation that doubles the periodicity of the lattice in the a-axis direction is observed. When the structure of LiFeBO3 is refined in the 4-dimensional superspace group C2/c(alpha 0 gamma)00, with alpha = 1/2 and gamma = 0 and with lattice parameters of a = 5.1681 angstrom, b = 8.8687 angstrom, c = 10.1656 angstrom, and beta = 91.514 degrees, all of the disorder present in the prior C2/c structural model is eliminated and a long-range ordering of 1D chains of corner-shared LiO4 is revealed to occur as a result of cooperative displacements of Li and O atoms in the c-axis direction. Solid-state hybrid density functional theory calculations find that the modulation stabilizes the LiFeBO3 structure by 1.2 kJ/mol (12 meV/f.u.), and that the modulation disappears after delithiation to form a structurally related FeBO3 phase. The band gaps of LiFeBO3 and FeBO3 are calculated to be 3.5 and 3.3 eV, respectively. Bond valence sum maps have been used to identify and characterize the important Li conduction pathways, and suggest that the activation energies for Li diffusion will be higher in the modulated structure of LiFeBO3 than in its unmodulated analogue.