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Steroid biomarkers provide evidence for a rapid rise of marine planktonic algae between 659 and 645 million years ago, establishing more efficient energy transfers and driving ecosystems towards larger and increasingly complex organisms.The transition from dominant bacterial to eukaryotic marine primary productivity was one of the most profound ecological revolutions in the Earth's history, reorganizing the distribution of carbon and nutrients in the water column and increasing energy flow to higher trophic levels. But the causes and geological timing of this transition, as well as possible links with rising atmospheric oxygen levels1 and the evolution of animals2, remain obscure. Here we present a molecular fossil record of eukaryotic steroids demonstrating that bacteria were the only notable primary producers in the oceans before the Cryogenian period (720-635 million years ago). Increasing steroid diversity and abundance marks the rapid rise of marine planktonic algae (Archaeplastida) in the narrow time interval between the Sturtian and Marinoan ‘snowball Earth' glaciations, 659-645 million years ago. We propose that the incumbency of cyanobacteria was broken by a surge of nutrients supplied by the Sturtian deglaciation3. The ‘Rise of Algae' created food webs with more efficient nutrient and energy transfers4, driving ecosystems towards larger and increasingly complex organisms. This effect is recorded by the concomitant appearance of biomarkers for sponges5 and predatory rhizarians, and the subsequent radiation of eumetazoans in the Ediacaran period2.