Bismuth tellurate nanospheres have been successfully synthesized by a facile hydrothermal route. X-ray diffraction (XRD) shows that the nanospheres are composed of orthorhombic Bi2Te2O7 phase. Scanning electron microscopy (SEM) displays that the diameter of the nanospheres is 100–500 nm. The bismuth tellurate nanospheres (BTS) modified glassy carbon electrode (GCE) has been prepared for the electrochemical detection of L-cysteine (L-CySH). A pair of semi-reversible CV peaks at +0.14 V and–0.84 V, respectively are observed. The BTS modified GCE displays high electrocatalytic activity toward L-CySH and exhibits a linear relationship in the range of 0.0001–2 mM with a detection limit of 0.046 μM in KCl solution. The broad linear range, low detection limit, good reproducibility and stability make the BTS modified GCE valuable for the practical application.