Crop cultivation has great potential to result in a phytolith carbon sink and can play important roles in the long-term stable carbon sequestration of terrestrial ecosystems. Buckwheat, an important multigrain crop with a very long cultivation history, is widely planted around the world. The phytolith carbon sink potential of buckwheat planting is still limited in the in-depth understanding of biogeochemical carbon sequestration in croplands. In order to estimate the phytolith carbon sink potential of buckwheat planting, in the present study, six species including 17 populations of Fagopyrum plants were selected as study materials. Firstly, their phytoliths were extracted using the wet oxidation method; then, the phytolith-occluded organic carbon (PhytOC) contents were determined using the spectrophotometry method; finally, the phytolith carbon sink potential of buckwheat planting was estimated. Results showed the following: 1) The PhytOC content range of the six Fagopyrum species studied was 0.006%~0.038%, which was significantly lower than that of rice, wheat, sugarcane, and some cereal and oil crops. There were significant differences in total silicon, phytolith, and PhytOC content of Fagopyrum plants among the different species, different organs (root, stem, and leaf), and different living forms (annual, partly perennial, and completely perennial). There were significant positive relationships between PhytOC and phytolith content and between phytolith and total silicon content. 2) The average phytolith carbon sequestration rate of Fagopyrum esculentum and Fagopyrum tataricum planting was 2.62 × 10-3 and 1.17 × 10-3 t CO2 hm-2·a-1, respectively, being approximately equal to that of terrestrial shrub vegetation. 3) The global total amount of phytolith carbon sequestration of buckwheat planting reached 5,102.09 t CO2 in 2018, and the Chinese total amount of phytolith carbon sequestration of buckwheat cultivation was 624.79 t CO2 in 2020. The phytolith carbon sink of buckwheat planting had significant potential for playing obvious roles in the carbon cycle. The present results are of great significance in crop phytolith studies and provide important references for phytolith carbon sink potential estimation of farmland ecosystems.