Abstract: A non-toxic sol–gel spin coating approach is one of the attractive routes to achieve high atom economy, good quality Cu2ZnSnS4 (CZTS) thin films. In this paper, we introduce 1,3-dimethyl-2-imadazolidinone as a solvent for the preparation of highly viscous, homogeneous, nontoxic CZTS ink that eliminates the need for the use of additional binders or additives to disperse the precursors. In addition, we further report the annealing of the spin coated CZTS thin film in 6% diluted H2S gas with an externally supplied tin and sulfur environment to suppress the loss of tin from the thin-film surface and to enhance the device performance. CZTS grain sizes greater than 0.7 μm have been achieved with no detectable presence of carbon rich layers or layers containing fine grain sizes at the Mo/CZTS interface. An efficiency of 5.67% for the champion device fabricated here has been achieved with an open circuit voltage of 0.58 V, a short current density of 18.48 mA cm−2, and a fill factor of 53.14%.