Fe(III) complexes have again attracted much attention for application as MRI contrast agents in recent years due to their high thermodynamic stability, low long-term toxicity, and large relaxivity at a higher magnetic field. This mini-review covers the recent progress on low-molecular-weight Fe(III) complexes, which have been considered as one of the promising alternatives to clinically used Gd(III)-based contrast agents. Two kinds of complexes including mononuclear Fe(III) complexes and multinuclear Fe(III) complexes are summarized in sequence, with a specific highlight of the structural relationships between the complexes and their relaxivity and thermodynamic stability. In additional, the future perspectives for the design of low-molecular-weight Fe(III) complexes for MRI contrast agents are suggested.