Thallium (Tl) is a nonessential and toxic trace metal that is detrimental to plants, but it can be highly up-taken in green cabbage (Brassica oleracea L. var. capitata L.). It has been proven that there is a significant positive correlation between Tl and Calcium (Ca) contents in plants. However, whether Ca presents a similar role for alleviating Tl toxicity in plants remains unclear, and little is known in terms of evidence for both Ca-enhanced uptake of Tl from soils to green cabbage and associated geochemical processes. In this study, we investigated the influence of Ca in soils on Tl uptake in green cabbage and the associated geochemical process. The pot experiments were conducted in 12 mg/kg Tl(I) and 8 mg/kg Tl(III) treatments with various Ca dosages. The results showed that Ca in soils could significantly enhance Tl uptake in green cabbage, increasing 210% in content over the control group. The soluble concentrations of Tl were largely increased by 210% and 150%, respectively, in 3.0 g/kg Ca treatment, compared with the corresponding treatment without Ca addition. This was attributed to the geochemical process in which the enhanced soluble Ca probably replaces Tl held on the soil particles, releasing more soluble Tl into the soil solution. More interestingly, the bioconcentration factor of the leaves and whole plant for the 2.0, 2.5, 3.0 g/kg Ca dosage group were greatly higher than for the non-Ca treatment, which could reach 207%, implying the addition of Ca can improve the ability of green cabbage to transfer Tl from the stems to the leaves. Furthermore, the pH values dropped with the increasing Ca concentration treatment, and the lower pH in soils also increased Tl mobilization, which resulted in Tl accumulation in green cabbage. Therefore, this work not only informs the improvement of agricultural safety management practices for the farming of crops in Tl-polluted and high-Ca-content areas, but also provides technical support for the exploitation of Ca-assisted phytoextraction technology.