In this study, we report Cu2ZnSn(S,Se)4 (CZTSSe) thin films synthesized by using a rapid thermal annealing process of direct current sputtered precursors under a sulfur and selenium atmosphere. X‐ray diffraction and Raman spectroscopy investigations showed formation of CZTSSe absorber layer without any secondary phase. X‐ray fluorescence spectroscopy showed a stoichiometric absorber layer has been formed which is suitable for use in solar cells. The best thin film solar cell of CZTSSe showed a photovoltaic performance of 5.2% efficiency (Voc: 585.0 mV, Jsc: 17.0 mA/cm2 and FF: 52.0%). This is the highest efficiency reported for CZTSSe prepared from sputtered Cu/Zn/Sn precursors followed by sulfo‐selenization using powder sources. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)