Dimethylformamide/dimethyl sulfoxide solvent mixtures were used as the CH3NH3PbI3 (MAPbI3) precursor solvent in a one-step spin coating method to fabricate smooth and hydrophilic crystalline MAPbI3 thin films on top of hydrophobic carbon-60 (C60) thin film for highly efficient photovoltaics. The structural, optical, and excitonic characteristics of the resultant MAPbI3 thin films were analyzed using X-ray diffraction (XRD), atomic-force microscopy, absorbance spectroscopy, photoluminescence (PL) spectrometry, and nanosecond time-resolved PL. There was a trade-off between the crystallinity and surface roughness of the MAPbI3 thin films, which strongly influenced the device performance of MAPbI3-based photovoltaics. The high power conversion efficiency (PCE) of 17.55% was achieved by improving the wettability of MAPbI3 precursor solutions on top of the C60 thin films. In addition, it was predicted that the fill factor and PCE could be further improved by increasing the crystallinity of the MAPbI3 thin film while keeping it smooth.