Here we demonstrate the fabrication of novel, “quasi-bilayer” inverted organic photovoltaic devices using halogen-free solvents. The inferior solubility of pristine fullerene in non-halogenated solvents was used to control the interpenetration of upper polymeric donor layers with bottom fullerene layers. Notably, island-like nano-morphologies were revealed by AFM, SEM, TEM, cross-sectional TEM images and PL quenching measurement. Correlation between device performance, thin-film nano-morphology and ac impedance was observed. High efficiencies of 6.55% and 7.15% were observed for PBDTTT-C-T and PTB7 cells, respectively. These results demonstrate that this novel process not only offers an effective new method to control the morphology of solar active layers but, more importantly, could also be applied to a wide range of current material systems to produce efficient devices that comply with the non-toxic halogen-free requirement.