Fluorine chemistry was demonstrated to show the importance of stretching the limits of chemical synthesis, oxidation state, and chemical bonding at ambient conditions. Thus far, the highest fluorine stoichiometry of a neutral first-row transition-metal fluoride is five, in VF5 and CrF5. Pressure can stabilize new stoichiometric compounds that are inaccessible at ambient conditions. Here, we attempted to delineate the fluorination limits of first-row transition metals at a high pressure through first-principles swarm-intelligence structure searching simulations. Besides reproducing the known compounds, our extensive search has resulted in a plethora of unreported compounds: CrF6, MnF6, FeF4, FeF5, FeF6, and CoF4, indicating that the application of pressure achieves not only the fluorination limit (e.g., hexafluoride) but also the long-sought bulky tetrafluorides. Our current results provide a significant step forward towards a comprehensive understanding of the fluorination limit of first-row transition metals.