Purpose: Occlusion of carbon (C) within phytoliths, biogenic silica deposited in plant tissues and returned to the soil, is an important mechanism for long-term terrestrial biogeochemical C sequestration and might play a significant role in mitigating climate change. Materials and methods: Subtropical and tropical soil profiles (to 100 cm depth) developed on granite and basalt were sampled using a mass-balance approach to explore the influence of climate and lithology on soil phytolith-occluded carbon (PhytOC) accumulation. Results and discussion: Soil PhytOC storage in the subtropics was significantly greater than in the tropics, with the soil profiles developed on granite storing greater PhytOC than soils derived on basalt. Phytolith and PhytOC content decreased with depth in all soil profiles. Phytolith content showed a positive correlation with the soil bio-available silicon in the soil profiles developed on basalt, while a negative correlation was observed in soil profiles developed on granite. Conclusions: Climate and lithology have a significant impact on soil PhytOC sequestration. The management of forests (e.g., afforestation and reforestation) and external silicon amendments (e.g., basalt powder amendment) in soils, especially those developed on granite, have the potential to enhance PhytOC accumulation in forest ecosystems.