Sunlight provides the energy required for all biochemical, physiological and developmental processes necessary for plant growth, reproduction and survival. The role of light in photosynthesis and photomorphogenesis has been appreciated for some time; however, the role of light in plant defence is a comparatively recent realization. Between 75–100 photosensitizers or phototoxins, molecules that become toxic in the presence of light, have been extracted from higher plant tissues. These biologically-active compounds have diverse biosynthetic origins and belong to at least 15 different phytochemical classes (i.e. acetophenones, acetylenes, benzophenanthrenes, β-carbolines, coumarins, extended quinones, furanochromones, furanocoumarins, furanoquinolines, isoquinolines, lignans, pterocarpans, quinolines, sesquiterpenes and thiophenes). Of more than 100 angiosperm families assayed, phototoxins and/or phototoxic activity have been reported in c. 40 families representing 32 orders and 8 subclasses of the Magnoliophyta. Most of these allelochemicals are acute toxins with little organism-specificity. As such, they are effective biocides capable of killing a wide-range of potentially harmful organisms including: viruses, pathogenic bacteria and fungi, nematodes and herbivorous insects, as well as competing plant species. This review focuses on the phytochemistry, taxonomic occurrence and toxicological consequences of phototoxic metabolites in flowering plants. The available information suggests that phototoxic phytochemicals: (i) are broad-spectrum allelochemicals capable of protecting plants against a variety of detrimental organisms in nature, (ii) represent a successful defensive strategy in both primitive and advanced plant taxa, and (iii) may be an effective defence under a variety of photoenvironmental conditions.