Doping properties of 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobifluorene (spiro-MeOTAD) hole transport layer are investigated by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and atomic force microscopy under air exposure. XPS results reveal that 3 h exposure of Li-bis(trifluoromethanesulfonyl)-imide (LiTFSI) doped spiro-MeOTAD to air results in the migration of LiTFSI from the bottom to the top across the spiro-MeOTAD film. AFM images reveal the presence of pinholes with an average diameter of ∼135 nm and a density of ∼3.72 holes/μm2. In addition, cross-sectional scanning electron microscope images reveal that these pinholes form channels across the doped spiro-MeOTAD film. Optical microscopy and Fourier transform infrared microscopy images confirm the presence of large pinholes with diameters in the range of 1-20 μm and a density of ∼289 holes/mm2 as well. The presence of pinholes may play a major role in the migration processes of the LiTFSI within the spiro-MeOTAD film as well as on the degradation processes of solar cells. This is further confirmed by the rapid decreasing efficiency of perovskite solar cells with solution prepared doped spiro-MeOTAD layers when exposed to air.