The release of highly toxic tellurite into the aquatic environment poses significant environmental risks. The acceleration mechanism and tellurium nanorods (TeNPs) characteristics with bioavailable ferric citrate (Fe(III)) were investigated in the tellurite (Te(IV)) bioreduction. Experiments showed that 5 mM Fe(III) increased the Te(IV) bioreduction rate from 0 to 12.40 mg/(L·h). Cyclic voltammetry, electrochemical impedance spectroscopy and Tafel were used to investigate electron transfer during Te(IV) bioreduction. NADH production (electron production) was significantly enhanced to 138% by Fe(III). Meanwhile Fe(III) stimulated the increase of cytochrome c, resulting in increased electron transport system activity. In addition, Fe(III) facilitated the secretion of extracellular polymeric substances (EPS) and reduced cell membrane permeability, thus reducing the toxicity of Te(IV) to cells. The increase of ATP provided energy for the metabolic process of Te(IV) bioreduction, playing an active role in cell activity. Based on the above analysis, the acceleration mechanism of Fe(III) on Te(IV) bioreduction was proposed from the aspects of electron generation, electron transfer and energy level. Zeta potential and FT-IR spectra indicated that the stability of TeNPs contributed to the covered EPS. This study provides further understanding the acceleration mechanism of Te(IV) bioreduction and promising strategy for improving the stability of TeNPs.