Silicon (Si) is beneficial to plants since it increases photosynthetic efficiency, and alleviates biotic and abiotic stresses. In the most highly weathered and desilicated soils, plant phytoliths make up the reservoir of bioavailable Si. The regular removal of crop residues, however, substantially decreases this pool. Si supply may therefore be required to sustain continuous cropping. Available Si fertilizers are costly and usually poor in soluble Si. Biochar produced from the pyrolysis of phytolith‐rich biomass is thus a promising alternative Si source for plants. Taking into account the challenges of increasing food demand and environmental concerns, we evaluate the global potential of biochar produced from major crop residues and manures in terms of phytogenic Si (PhSi) supply. Crop residues contribute to 80% of the global production of biomass dry matter (8,201 Tg/year) of which 3,137 Tg/year are potentially available after pyrolysis, giving a potential application rate of 1.7 T ha⁻¹ year⁻¹ for highly weathered soils in the tropics. The potential PhSi supply from crop biochar amounts to 102 Tg Si/year. On its own, rice straws produce 57.7 Tg PhSi/year, accounting for 56.6% of the potential annual PhSi production. The Si release from crop biochar depends on inter altere feedstock type, pyrolysis temperature, soil pH, and buffer capacity. Furthermore, the amplitude of plant Si uptake and mineralomass depends on plant species, soil properties, and processes. These factors interact and can exert a decisive influence on the effectiveness of phytolithic biochar in releasing Si into highly weathered soils. We conclude that the use of phytolithic biochar as a Si fertilizer offers undeniable potential to mitigate desilication and to enhance Si ecological services due to soil weathering and biomass removal. This potential must be explored, as well as the conditions for using biochar in the field.