The biogeochemical silicon cycle influences global primary productivity and carbon cycling, yet changes in silicon sources and cycling during long-term development of terrestrial ecosystems remain poorly understood. Here, we show that terrestrial silicon cycling shifts from pedological to biological control during long-term ecosystem development along 2-million-year soil chronosequences in Western Australia. Silicon availability is determined by pedogenic silicon in young soils and recycling of plant-derived silicon in old soils as pedogenic pools become depleted. Unlike concentrations of major nutrients, which decline markedly in strongly weathered soils, foliar silicon concentrations increase continuously as soils age. Our findings show that the retention of silicon by plants during ecosystem retrogression sustains its terrestrial cycling, suggesting important plant benefits associated with this element in nutrient-poor environments.