To commercialize Cu2ZnSn(S,Se)(4) (CZTSSe) thin-film solar cells, it is necessary to improve their efficiency and to develop the technological ability to produce large-area modules. Defect formation due to the secondary phase is considered to be one of the main reasons for decreased CZTSSe thin-film solar-cell efficiency. This study explores the potential capabilities of large-area thin-film solar cells by controlling the defect formation using various CZTSSe precursor designs, and by improving the characteristic uniformity within the thin-film solar cells. Alloying the precursor as a stack of discrete layers can result in lateral segregation of elements into stable-phase islands, yielding a non-uniform composition on small length scales. It is found that the application of an indiscrete layer by minimizing the precursor-layer thickness allows avoiding Zn rich inhomogeneities in the absorber that would favor formation of detrimental ZnS-ZnSe secondary phases and deep defects. Among the various precursor layers designed by considering the reaction mechanism under annealing, a sample with 15 precursor layers is found to exhibit a shallow electron-acceptor energy level, high photovoltaic conversion efficiency, and uniform characteristics over the corresponding thin-film solar cell. Based on such improvements in both the efficiency and characteristic distribution, it is expected that the commercialization of CZTSSe thin-film solar cells can be advanced.