A set of three N,N-di-p-methoxyphenylamine-substituted pyrene derivatives have successfully been synthesized and characterized by H-1/C-13 NMR spectroscopy, mass spectrometry, and elemental analysis. The optical and electronic structures of the pyrene derivatives were adjusted by controlling the ratio of N,N-di-p-methoxyphenylamine to pyrene, and investigated by UV/vis spectroscopy and cyclic voltammetry. The pyrene derivatives were employed as hole-transporting materials (HTMs) in fabricating mesoporous TiO2/CH3NH3PbI3/HTMs/Au solar cells. The pyrene-based derivative Py-C exhibited a short-circuit current density of 20.2 mA/cm(2), an open-circuit voltage (V-oc) of 0.886 V, and a fill factor of 69.4% under an illumination of 1 sun (100 mW/cm(2)), resulting in an overall power conversion efficiency of 12.4%. The performance is comparable to that of the well-studied spiro-OMeTAD, even though the V-oc is slightly lower. Thus, this newly synthesized pyrene derivative holds promise as a HTM for highly efficient perovskite-based solar cells.