The nano-zero-valent iron composite (nZVI@TP-Mont) was successfully prepared using a low-cost and environmental-friendly green synthesis via tea leaves extract (tea polyphenols, TPs) and the montmorillonite (Mont). The batch and column experiments and characterization were conducted to investigate the transport behavior and Cr(VI) remediation by nZVI@TP-Mont in water/soil. Due to its particular surface characteristics and morphology (i.e., the Fe0 core wrapped by TPs, the doped sulfur, and interlayer structure), the nZVI@TP-Mont composite showed a great removal capacity of Cr(VI) and sufficient mobility under different soil conditions. We opine the increase in the Cr(VI) reduction of nZVI@TP-Mont was attributed to the tethering of Fe2O3 on the surface of Fe0 core by the support of Mont interlayer, especially the TP-coverage around nZVI@TP-Mont surface unwrapped, thereby increasing the regenerated reactive Fe2+ and the exposed reaction sites of Fe0 cores to Cr(VI). The increased transportability of nZVI@TP-Mont slightly depends on the heterogeneous soil properties (i.e., ionic strength, sand/soil ratio, and pH). The two-site kinetic attachment model fitting results suggest Cr(VI)/Cr(III) speciation associated with the agglomerated nZVI@TP-Mont were efficiently immobilized in soil. Therefore, this study would benefit the efficient application of the green-synthesized nZVI@TP-Mont in in-situ remediation of soils contaminated by Cr(VI).