To simultaneously promote biomass yield and astaxanthin content of Haematococcus pluvialis, ammonium ferric citrate (AFC) was employed to stimulate light harvest in photosynthesis during the green stage and oxidation induction in astaxanthin accumulation during the red stage. AFC not only improved chlorophyll synthesis by 22.5% to provide more electrochemical potential energy in the green stage, but also alleviated photosystem II damage to maintain a high level of effective quantum yield by enhancing carotenoid production. The citrate derived from AFC stimulated acetyl-CoA and NADPH production through citric acid cycle and transaminase cycle during the red stage, resulting in an increased lipid content by 1.77-fold. The astaxanthin content in H. pluvialis cells cultivated with 5 μM AFC was 12.5% higher than that without AFC, which was attributed to severe oxidative stress caused by AFC through Haber-Weiss reaction. These results provided a new approach to reduce emission of greenhouse gasses with producing high-value products.