Phytoplankton have a high potential for CO 2 capture and conversion. Besides being a vital food source at the base of oceanic and freshwater food webs, microalgae provide a critical platform for producing chemicals and consumer products. Enhanced nutrient levels, elevated CO 2 , and rising temperatures increase the frequency of algal blooms, which often have negative effects such as fish mortalities, loss of flora and fauna, and the production of algal toxins. Harmful algal blooms (HABs) produce toxins that pose major challenges to water quality, ecosystem function, human health, tourism, and the food web. These toxins have complex chemical structures and possess a wide range of biological properties with potential applications as new therapeutics. This review presents a balanced and comprehensive assessment of the roles of algal blooms in generating fixed carbon for the food chain, sequestering carbon, and their unique secondary metabolites. The structural complexity of these metabolites has had an unprecedented impact on structure elucidation technologies and total synthesis, which are highlighted throughout this review. In addition, the influence of biogeochemical environmental perturbations on algal blooms and their influence on biospheric environments is discussed. Lastly, we summarize work on management strategies and technologies for the control and treatment of HABs.