Early and accurate diagnosis of hepatocellular carcinoma (HCC) is of great significance to improve the treatment effect and prolong the survival rate of patients with HCC. At present, magnetic resonance imaging (MRI) is still an important tool for the early diagnosis of HCC, but due to the lack of MRI probes with high specificity and sensitivity, its early clinical diagnosis of HCC is poor, especially for the micron-sized HCC (mHCC). Here, we successfully constructed magnetic nanoassemblies (Cr-ESIONP) with efficient GSH-responsive MR signal switching function by optimizing the conditions, which is composed of extremely-small iron oxide nanoparticles (ESIONP) crosslinked by disulphide bonds, and can be disassembled by GSH to realize the switch from T2 MR signal to T1 MR signal. Based on the effective liver uptake of Cr-ESIONP and the significant difference in GSH content between normal liver tissue and tumor tissue, we successfully verified the excellent specificity of CrESIONP in the diagnosis of mHCC in vivo MRI experiments. Further in vivo MRI experiments proved that CrESIONP had a higher detection rate for mHCC than clinical Gd-DTPA. Excellent in vitro and in vivo performance indicates that Cr-ESIONP is a new type of HCC specific MR contrast agent with great potential for clinical application.