The thermal expansion, structural changes and the site partitioning of Co and Mg in synthetic CoMg- SiO4 olivine have been studied by in situ time-of-flight neutron powder diffraction as a function of temperature, between 25 and 1,000C. Thermal expansion of the unit cell dimensions and volume are linear within this temperature range and give no indications of a phase transition, although the thermoelastic behaviour indicates a slight strain minimum around 700C. Co2+ shows a strong preference for the M1 site throughout this temperature range with an oscillatory behaviour; it decreases slightly at about 300C, climbing up to nearly its original value at around 800C and then decreasing by about 30% at 1,000C. This behaviour is in contrast with that of (Fe, Mg)2SiO4 olivine, in which the initial Fe2+ site preference for the M1 site switches to the M2 site beyond a cross-over temperature. The oscillatory site preference in (CoMg)-olivine as a function of temperature is reflected in the M–O polyhedral volume changes and M–O bond lengths, as well as, thermoelastic strain and atomic thermal displacement parameters. The imbalance between the increasing vibrational and decreasing configurational entropy contributions, together with covalent bonding effects rather than crystal field contributions, seem to drive the cation partitioning in (CoMg)-olivine.