Selenium (Se) isotopes can yield substantial isotopic fractionation (up to 20‰) confirmed by experiments and field investigations, depending on various biotic or abiotic redox transformations. Therefore, it is expected that redox changes in the ancient oceans would induce significant isotopic fractionation, and the Se isotopic signatures recorded in old sedimentary rocks might provide new insight into how the redox state of the ancient ocean has evolved. However, previous studies have shown that Se is slightly enriched in the lighter isotope relative to the bulk earth values in most deposited conditions (oxic, anoxic, and even sulfidic). Here, our results reveal that ferruginous conditions can result in excessive accumulation of Se in sediments with an elevated Se/S ratio and significant isotope fractionation (about 6‰), which leads us to propose that Se isotopes are an appropriate geochemical proxy to trace unique oceanic conditions over times. Accordingly, Se isotopic variations measured in three Early Cambrian formations in southern China suggest that anoxic waters with ferruginous conditions must have been present in early Cambrian ocean along the eastern margin of the Yangtze platform, and oceanic circulation was stepwise reorganized. This may have triggered biological diversification from the Ediacaran to the Early Cambrian.