The Early Phanerozoic witnessed one of the most important events in Earth history - the Cambrian Explosion. There is also a consensus that at roughly the same time oceanic dissolved silicon (DSi) concentrations decreased from close to saturation to somewhere below saturation. Yet the timing and magnitude of the putative DSi decrease, and any relationship with biological innovations, remain poorly known. Here, we study the widespread chert formed during the Ediacaran-Cambrian transition (ca. 551-522 Ma) on the Yangtze Block, South China. Major and trace element geochemistry suggest the silicon for the chert is predominantly sourced from seawater, and most likely precipitated via adsorption on organic matter and uptake by silica-secreting organisms. New and compiled silicon isotope data from seven sections spanning the E-C boundary show an increase in divergence of ${\delta }^{30}$Si values at ca. 533 Ma. Using mass-balance arguments, we interpret this as evidence that the radiation of siliceous sponges and radiolarians contributed to a substantial (ca. 80%) decrease in oceanic DSi concentrations, which is corroborated by fossil records and simple box-models. Reduced oceanic DSi may reduce the effort needed to maintain intracellular Si concentrations below the level at which harmful Si precipitation in organismal cytoplasm occurs. This energy can be reallocated to other metabolic pathways of new functional types, potentially the establishment of suspension-feeding communities that triggered Phanerozoic-type mixground ecology. Therefore, the early appearance of silicifiers (∼540-530 Ma) may have made conditions more favorable for the main stage (∼520 Ma) of Cambrian Explosion in functional and ecological diversification.