Methods for synthesising fluoro-organic compounds with the aid of thermolytic processes are discussed. High-temperature transformations of fluorinated saturated and unsaturated compounds, as well as of aromatic and heterocyclic compounds are considered. 1. Thermolysis of Saturated Compounds 1.1. Alkanes 1.2. Cycloalkanes 1.3. Fluorinated Polymers 2. Thermolysis of Unsaturated Compounds 2.1. Alkenes and Alkynes 2.2. Cycloalkenes 2.3. Thermolysis of Unsaturated Compounds in the Presence of Difluorocarbene Sources 3. Thermolysis of Aromatic and Heterocyclic Compounds 3.1. Aromatic and Heterocyclic Compounds 3.2. Reactions with Polytetrafluoroethene and Potassium Fluoride 3.3. Reactions with Fluoroalkenes 3.3.1. Hexafluorobenzene (F-Benzene) 3.3.2. Reactions of Compounds with Functional Groups 3.4. Reactions with Sources of Radicals 4. Other Reactions 4.1. Pyrolysis of Carboxylic Acids and their Derivatives 4.2. Miscellaneous Reactions