Visualization of biomolecules, cells, and tissues, as well as metabolic processes in vivo is significant for studying the associated biological activities. Fluorine magnetic resonance imaging (19F MRI) holds potential among various imaging technologies thanks to its negligible background signal and deep tissue penetration in vivo. To achieve detection on the targets with high resolution and accuracy, requirements of high‐performance 19F MRI probes are demanding. An ideal 19F MRI probe is thought to have, first, fluorine tags with magnetically equivalent 19F nuclei, second, high fluorine content, third, adequate fluorine nuclei mobility, as well as excellent water solubility or dispersity, but not limited to. This review summarizes the research progresses of 19F MRI probes and mainly discusses the impacts of structures on in vitro and in vivo imaging performances. Additionally, the applications of 19F MRI probes in ions sensing, molecular structures analysis, cells tracking, and in vivo diagnosis of disease lesions are also covered in this article. From authors’ perspectives, this review is able to provide inspirations for relevant researchers on designing and synthesizing advanced 19F MRI probes.