We report the synthesis and characterization of Cu2ZnSnS4 (CZTS) with controlled phase purity. The precursor was first prepared using sequential electrodeposition of Cu, Zn, and Sn in different orders. The Cu/(Sn+Zn) ratio in each stacking order was also varied. The precursor was subjected to annealing at 200°C and sulfurization at 500°C in a 5%-H2S/Ar atmosphere for the formation of CZTS. The phase evolutions during the electrodeposition and annealing stages, and the final phase formation at the sulfurization stage were examined using both x-ray diffractometry and Raman spectroscopy, both of which are shown to be complimentary tools for phase identification. Detailed growth path is therefore reported. We also demonstrate by controlling the stacking order and the Cu/(Sn+Zn) ratio, CZTS with a phase purity as high as 93% is obtained.