Pruned tea leaves are discarded or burned as agricultural residue, causing resource waste and serious environmental problems. Pruned tea leaves with a rich number of cellulosic and polyphenolic components could be used as biomass feedstocks and reducing agents to synthesize ZVI-embedded biochar. In this work, a green, inexpensive and convenient method was developed for the synthesis of nanoscale zero-valent iron embedded biochar (TLBC-nZVI) using pruned tea leaves. TLBC-nZVI showed excellent performance in Cr(VI) removal (166.65 mg g−1) from aqueous solutions. Isothermal, kinetic and thermodynamic studies showed that Cr(VI) removal fit well with the Freundlich model and pseudo-second order model. Additionally, the removal process was a chemical, spontaneous and endothermic reaction. The removal mechanisms were as follows: (i) protonated TLBC-nZVI adsorbed anionic Cr(VI) by electrostatic interaction under acidic conditions; (ii) Fe0, Fe(II) and some surface functional groups (such as –NH2 and –OH) reduced Cr(VI) to Cr(III); and (iii) Cr(III) was removed through complexation, physical adsorption and coprecipitation.