The band structures of ordered and thermally disordered Li2Mo12O34 are calculated by use of the ab initio density-functional-theory–linear-muffin-tin (DFT-LMTO) method. The unusual, very one-dimensional band dispersion obtained in previous band calculations is confirmed for the ordered structure, and the overall band structure agrees reasonably well with existing photoemission data. Dispersion and band structure perpendicular to the main dispersive direction are obtained. A temperature-dependent band broadening is calculated from configurations with thermal disorder of the atomic positions within the unit cell. This leads to band broadening of the two bands at the Fermi energy which can become comparable to their energy separation. The bands are particularly sensitive to in-plane movements of Mo sites far from the Li sites, where the density of states (DOS) is highest. The latter fact makes the effect of Li vacancies on the two bands relatively small. Spin-polarized band results for the ordered structure show a surprisingly large exchange enhancement on the high DOS Mo sites. Consequences for spin fluctuations associated with a cell doubling along the conducting direction are discussed.