Whilst the corrosion protection of steel in aqueous chloride environments by the rare earth inhibitor lanthanum 4-hydroxycinnamate is well known, the influence of the structural variation of the organic component as well as the nature of the metal centre has not previously been addressed. Herein we show that praseodymium 4-hydroxy cinnamate is comparable to its lanthanum counterpart in aqueous solution. On the other hand, cerium 4-hydroxycinnamate and lanthanum 2-hydroxycinnamate show poor corrosion protection performance while lanthanum 3-hydroxycinnamate provides a level of inhibition between these. These differences are shown to be related to the speciation in solution and are postulated to be linked to steric influences which are likely to affect the bonding environment within the rare earth compound itself, as well as its bonding with the steel substrate.