Medical imaging contrast agents that are able to provide detailed biological information have attracted increasing attention. Among the new emerging imaging contrast agents, ¹⁹F magnetic resonance imaging contrast agents (¹⁹F MRI CAs) are extremely promising for their weak background disturbing signal from the body. However, to prepare ¹⁹F MRI CAs with a long T₂ relaxation time and excellent biocompatibility in a simple and highly effective strategy is still a challenge. Herein, we report a new type of ¹⁹F MRI hydrogel nanocontrast agents (¹⁹F MRI HNCAs) synthesized by a surfactant-free emulsion polymerization with commercial fluorinated monomers. The T₂ relaxation time of ¹⁹F MRI HNCA-1 was found to be 25–40 ms, guaranteeing its good imaging ability in vitro. In addition, according to an investigation into the relationship between the fluorine content and ¹⁹F MRI signal intensity, the ¹⁹F MRI signal intensity was not only determined by the fluorine content in ¹⁹F MRI HNCAs but also by the hydration microenvironment around the fluorine atoms. Moreover, ¹⁹F MRI HNCAs demonstrated excellent biocompatibility and imaging capability inside cells. The primary exploration demonstrated that ¹⁹F MRI HNCAs as a new type of ¹⁹F MRI contrast agent hold potential for imaging lesion sites and tracking cells in vivo by ¹⁹F MRI technology.