Hybrid organic-inorganic perovskite materials have risen up as leading components for light-harvesting applications. However, to date many questions are still open concerning the operation of perovskite solar cells (PSCs). A systematic analysis of the interplay among structural features, optoelectronic performance, and ionic movement behavior for FA0.83 MA0.17 Pb(I0.83 Br0.17 )3 PSCs is presented, which yield high power conversion efficiencies up to 20.8%.