Fully synthetic, biochemically inert and water-immiscible liquid perfluorochemicals (PFCs) are recognised as flexible liquid carriers/scavengers of gaseous compounds (respiratory gases mainly, i.e. O2 and CO2) and increasingly applied in bioprocess engineering. A range of unmatched physicochemical properties of liquid PFCs, i.e. outstanding chemo- and thermostability, extremely low surface tension, simultaneous hydro- and lipophobicity, which result from carbon chain substitution with fluorine atoms (the most electronegative chemical element) and the presence of intramolecular C-F bonds (the strongest single bond known in organic chemistry) have been described in detail. Exceptional propensity to solubility of respiratory gases in liquid perfluorinated compounds has been widely discussed. Advantages and disadvantages of bioprocess applications of liquid PFCs in the form of a pure PFC as well as in an emulsified form have been pointed out. A liquid PFC-mediated mass transfer intensification in various types of microbial, plant cell and animal cell culture systems: from miniaturised microlitre-scale cultures, via biomaterial-based scaffolds containing culture systems, to litre-scale bioreactors, has been reviewed and elaborated on bearing in mind the benefits of bioprocesses.