Three spiro-OMeTAD derivatives have been synthesized and characterized by (1)H/(13)C NMR spectroscopy and mass spectrometry. The optical and electronic properties of the derivatives were modified by changing the positions of the two methoxy substituents in each of the quadrants, as monitored by UV-vis spectroscopy and cyclic voltammetry measurements. The derivatives were employed as hole-transporting materials (HTMs), and their performances were compared for the fabrication of mesoporous TiO2/CH3NH3PbI3/HTM/Au solar cells. Surprisingly, the cell performance was dependent on the positions of the OMe substituents. The derivative with o-OMe substituents showed highly improved performance by exhibiting a short-circuit current density of 21.2 mA/cm(2), an open-circuit voltage of 1.02 V, and a fill factor of 77.6% under 1 sun illumination (100 mW/cm(2)), which resulted in an overall power conversion efficiency (PCE) of 16.7%, compared to ~15% for conventional p-OMe substituents. The PCE of 16.7% is the highest value reported to date for perovskite-based solar cells with spiro-OMeTAD.