Cyanotoxin-producing harmful algal blooms (HABs) are a global occurrence and pose ecotoxicological threats to humans and animals alike. The presence of cyanotoxins can seriously harm or kill nearby wildlife and restrict a body of water's use as a drinking water supply and recreational site, making it imperative to fully understand their fate and transport in natural waters. Photodegradation contributes to the overall degradation of cyanotoxins in environmental systems, especially for those present in the photic zone of surface waters. This makes photochemical transformation mechanisms important factors to account for when assessing the persistence of cyanotoxins in environmental systems. This paper reviews current knowledge on the photodegradation rates and pathways of cyanotoxins that can occur over the course of HABs. Sensitized, or indirect, photolysis contributes to the degradation of all cyanotoxins addressed in this paper (anatoxins, cylindrospermopsins, domoic acids, microcystins, and nodularins), with hydroxyl radicals (•OH), excited triplet states formed from the absorption of light by dissolved organic matter (3DOM*), and photosynthetic pigment sensitized pathways being of primary interest. Direct photolysis pathways play a less significant role, but are still relevant for most of the cyanotoxins discussed in this paper.