Abstract Organometal trihalide perovskite solar cells have recently attracted lots of attention in the photovoltaic community due to their escalating efficiency and solution processability. The most efficient organometallic mixed-halide sensitized solar cells often employ 2,2′7,7′-tetrakis-( N , N -di- p -methoxyphenyl-amine)-9,9′-spirobifluorene (spiro-MeOTAD) as the hole-transporting material. In this work, we investigated the effect of different atmospheric storage conditions, particularly vacuum, dry nitrogen, and dry air, on the photovoltaic performance of TiO 2 –CH 3 NH 3 PbI 3− x Cl x –spiro-MeOTAD solar cells. We found that spin coating of spiro-MeOTAD in an oxygen atmosphere alone was not adequate to functionalize its hole-transport property completely, and our systematic experiments revealed that the device efficiency depends on the ambient atmospheric conditions during the drying process of spiro-MeOTAD. Complementary incident photon to current conversion efficiency (IPCE), light absorption and photoluminescence quenching measurements allowed us to attribute the atmosphere-dependent efficiency to the improved electronic characteristics of the solar cells. Furthermore, our Fourier transform infrared and electrical impedance measurements unambiguously detected modifications in the spiro-MeOTAD after the drying processes in different gas environments. Our findings demonstrate that proper oxidization and p-doping in functionalizing spiro-MeOTAD play a very critical role in determining device performance. These findings will facilitate the search for alternative hole-transporting materials in high-performance perovskite solar cells with long-term stability.