The activation and functionalization of carbon–fluorine bonds can be considered as a major challenge in organometallic chemistry. The growing demand for means to introduce fluorine into new materials or into biologically active molecules has inspired the development of diverse synthetic strategies. Hydrodefluorination is regarded as a promising approach to access partially fluorinated building blocks from readily available perfluorinated bulk chemicals. We provide an overview of transition-metal-based complexes and catalysts that were developed to mediate hydrodefluorination reactions. Special emphasis will be placed on discussing the underlying mechanistic patterns and their impact on scope and selectivity. In addition, future requirements for further developing this field will be highlighted.