The use of fluoro substituents in liquid crystals has proved essential for the development of materials with optimised properties for advanced high technology devices. The small size and high polarity of a fluoro substituent can have some remarkable effects on the important physical properties of liquid crystals. Fluoro substituents can be usefully located at many different sites of a liquid crystal structure. Such a wide variety of possibilities allows for the advantageous tailoring of physical properties to meet the exacting demands of the various formats of application. This paper considers in detail the fascinating influence that fluoro substituents in the various locations have on these vital properties, and looks at some of the interesting aspects of the synthesis of such materials.