Pure monoclinic single crystalline Ag2Te nanorods were synthesized by a two-step method. The first step concerns the electrodeposition of self-standing Te nanorods in an ionic liquid medium, taking advantage of its templating properties. These obtained nanorods are single crystalline with growth direction along the [001] axis in the hexagonal lattice. The average diameter of the as-deposited Te nanorods is 60 ± 13 nm with less than 300 nm long. Afterwards, the resulting nanostructured Te film is immerged in a dedicated silverbased bath in order to be transformed into Ag2Te binary compounds by a combined mechanism of chemical cementation and topotactic transformation. The chemical analysis reveals that the final nanostructures exhibit a slight excess of silver and TEM-SAED analysis shows that they are still single crystalline with an increase of the initial diameter, less than 30%. HR-TEM highlights the presence of an intermediate stützite phase and the hessite phase α-Ag2Te is obtained at the end of the synthesis process.