A nanocrystalline Sb2Te3 VA-VIA group compound thin film was grown via the route of electrochemical atomic layer epitaxy (ECALE) in this work for the first time. The electrochemical behavior of Te and Sb on Pt, Te on Sb-covered Pt, and Sb on Te-covered Pt was studied by methods of cyclic voltammetry, anode potentiodynamic scanning, and coulometry. A steady deposition of the Sb2Te3 compound could be attained after negatively stepped adjusting of the UPD potentials of Sb and Te on Pt in each of the first 40 depositing cycles. The structure of the deposit was proven to be the Sb2Te3 compound by X-ray diffraction. The 2:3 stoichiometric ratio of Sb to Te was verified by EDX quantitative analysis, which is consistent with the result of coulometric analysis. A nanocystalline microstructure was observed for the Sb2Te3 deposits, and the average grain size is about 20 nm. Cross-sectional SEM observation shows an interface layer about 19 nm in thickness sandwiched between the Sb2Te3 nanocrystalline deposit and the Pt substrate surface. The optical band gap of the deposited Sb2Te3 film Was determined as 0.42 eV by FTIR spectroscopy and it is blueshifted in comparison with that of the bulk Sb2Te3 single crystal because of its nanocrystalline microstructure.