Main conclusion <p>A comprehensive view of redox properties of quinones has demonstrated how prenylquinonones define the operation of photosynthetic electron transfer in thylakoids.</p> <p>The synthetic quinones play an analogous role in photosynthesis research and biophotovoltaic devices.</p> Abstract <p>The para-quinones are an enormous group of small organic molecules assembled from benzoquinone core and two carbonyl groups that may be reduced to hydroxyl groups by accepting two electrons and two protons. Their redox properties depend on types of attached functional groups and are strongly influenced by the surrounding environment. The process of their reduction/oxidation may occur in multiple stages by specific molecular species that differ in electrochemical properties. These properties make quinones versatile molecules mediating the protons-coupled electrons transfer both in natural and artificial systems. Particularly noteworthy are isoprenoid quinones (prenylquinones) playing a pivotal role in photochemical reactions of photosystems and coupling the lateral electron transfer with vertical proton pumping in photosynthetic membranes. The importance of prenylquinonones is usually described independently of each other with respect to the functioning of individual photosynthetic complexes. Therefore, in this review we have collected scattered information in concise but detailed form, focusing on how the molecular and redox properties of prenylquinonones define the operation of plant Photosystems I, II and cyt <i>b</i>₆<i>f</i> complexes and the plastoquinone pool associated H⁺/e^– transfer’s pathways as well as non-enzymatic generation and scavenging of reactive oxygen species. We also referred to the biosynthesis of prenylquinonones and the diversity of their forms found in plastid membranes. Finally, we described the use of synthetic quinone derivatives in the study of natural photosynthesis and biophotovoltaic devices.</p>