Stable and nontoxic bismuth iodide (BiI3) is emerging as a promising absorber material for solar cell applications as it possesses favorable optical properties such as a narrow bandgap (1.7 eV) and a high absorption coefficient (105 cm–1) in the visible region. Despite these promising features, solar cells employing this material have only achieved power conversion efficiencies in the region of 1% as of yet, which is distant from the theoretical efficiency limit of 28%. It is reasonable to suppose that the relatively low performance of BiI3-based solar cells may originate from very short carrier lifetimes (180–240 ps) in BiI3, which makes efficient separation of mobile charges a crucial factor for the improvement of the photovoltaic performance of this material. Herein, transient optical spectroscopy is employed to show that the use of a bismuth sulfide iodide interlayer between the electron transport layer (ETL) and the bismuth iodide absorber promotes efficient charge separation. On the basis of this knowledge, we report BiI3 solar cells with a power conversion efficiency of 1.21% using a solar cell architecture comprised of ITO/SnO2/BiSI/BiI3/organic HTM/Au
