This study reports a multifunctional nanoparticle (NP) that can be used for amplified magnetic resonance image (MRI)-guided photothermal therapy (PTT) due to its surface coating with a polydopamine (PDA) shell. Importantly, by means of introducing the surface coating of PDA, large quantities of water can be trapped around the NPs allowing more efficient water exchange, leading to greatly improved MR contrast signals compared with those from NPs without the PDA coating. Further, a distinct photothermal effect can be obtained arising from the strong absorption of PDA in the near-infrared (NIR) region. By synthesizing multifunctional MnCO@PDA NPs, for example, we found that the longitudinal relaxivity (r) of MnCO NPs can improve from 5.7 to 8.3 mM s. Subsequently, in vitro MRI and PTT results verified that MnCO@PDA could serve as an excellent MRI/PTT theranostic agent. Furthermore, the MnCO@PDA NPs were applied as an MRI/PTT theranostic agent for in vivo MRI-guided photothermal ablation of tumors by intratumoral injection in 4T1 tumor-bearing mice. The MR imaging result shows a significantly bright MR image in the tumor site. The MnCO@PDA-mediated PTT result shows high therapeutic efficiency as a result of high photothermal conversion efficiency. The present strategy of amplified MRI-guided PTT based on PDA coating of NPs will be widely applicable to other multifunctional NPs.