Laser annealing is an attractive process to form high-quality semiconductor films because of localized annealing area and short annealing time. In a previous study, a Cu2ZnSnS4 (CZTS) polycrystalline semiconductor film was realized using laser annealing in air as a light absorption layer for solar cells, although the crystallization was not sufficient in comparison with CZTS formed by the conventional thermal sulfurization process. In this study, we demonstrate a newly developed gas-atmosphere-controlled laser annealing system. A Cu–Zn–Sn–S-based precursor was formed, followed by laser annealing of the system. Laser annealing in air, Ar, and 5% H2S/Ar gas was performed to investigate the influence of the gas species on the crystallization of the precursor. A 5% H2S/Ar atmosphere promoted the crystallization of CZTS with the suppression of S desorption and Cu sulfide formation, while air and Ar atmospheres allowed the formation of Cu sulfide.