Global optimization and density functional theory-based calculations are used to investigate the structure of (TiC)6 and (TiC)12 clusters. In both cases, the isomers exhibiting the bulk-like rock salt structure appear to be the most energetically stable. This is in contrast to a number of other materials that have the rock salt structure as their bulk ground state, such as MgO, for which more open tubular motifs are observed. A major factor contributing to this difference in nanoscale structure is likely to be the larger covalent character of TiC as compared to MgO. This is supported by our finding that some of the low-energy isomers of both (TiC)6 and (TiC)12 exhibit C–C bonding, whereas the bonding in all analogously sized MgO isomers is solely based on Mg–O ionic bonding. The simulated IR spectra indicate that it should be experimentally possible to differentiate (TiC) n clusters with or without C–C bonds.