Azolla is the only plant with a co-evolving nitrogen-fixing (diazotrophic) cyanobacterial symbiont (cyanobiont), Nostoc azollae, resulting from Whole Genome Duplication (WGD) 80 million years ago in Azolla’s ancestor. Additional genes from the WGD resulted in genetic, biochemical and morphological changes in the plant that enabled transmission of the cyanobiont to successive generations via its megaspores. The resulting permanent symbiosis and co-evolution led to loss, downregulation or conversion of non-essential genes to pseudogenes in the cyanobiont, changing it from a free-living organism to an obligate symbiont. Upregulation of other genes in the cyanobiont increased its atmospheric dinitrogen fixation and provision of nitrogen-based products to the plant. As a result, Azolla can double its biomass in less than two days free-floating on fresh water and sequester large amounts of atmospheric CO2, giving it the potential to mitigate anthropogenic climate change through Carbon Capture and Storage. Azolla’s biomass can also provide local, low-cost food, biofertiliser, feed and biofuel that are urgently needed as our population increases by a billion every twelve years. This paper integrates data from biology, genetics, geology and paleontology to identify the location, timing and mechanism for the acquisition of a co-evolving diazotrophic cyanobiont by Azolla’s ancestor in the Late Cretaceous (Campanian) of North America.