This critical review begins with a brief, but essential, introduction to the special nature of liquid crystal materials, their peculiar properties, and their commercial applications, followed by an introductory insight into the remarkable nature of the fluoro substituent, and its fascinating influence on the properties of organic compounds. However, the main focus of the review is to discuss the enormous amount of exciting research on fluorinated liquid crystals that has been reported. The small size of the fluoro substituent enables its incorporation into all types of liquid crystal, including calamitic, discotic, banana, lyotropic, and polymers, without ruining the liquid crystalline nature of the material. However the fluoro substituent is larger than hydrogen, and hence causes a significant steric effect, which combined with the high polarity, confers many fascinating, and often remarkable, modifications to melting point, mesophase morphology and transition temperatures, and the many other very important physical properties, such as dielectric anisotropy, optical anisotropy, and visco-elastic properties. There are many different positions within a liquid crystal structure where a fluoro substituent can be located, including (i) a terminal position, (ii) within a terminal chain, as a semi-fluorinated or as a perfluorinated chain, or as one fluoro substituent at a chiral centre, (iii) as part of a linking group, and (iv) a lateral position in the core section. Such variety enables the interesting and advantageous tailoring of properties, both for the fundamental purposes of establishing structure–property relationships, and for materials targeted towards commercially-successful liquid crystal display applications.