The photovoltaic performance of perovskite solar cells (PVSCs) is extremely dependent on the morphology and crystallization of the perovskite film, which is affected by the deposition method. In this work, a new approach is demonstrated for forming the PbI2 nanostructure and the use of high CH3NH3I concentration which are adopted to form high-quality (smooth and PbI2 residue-free) perovskite film with better photovoltaic performances. On the one hand, self-assembled porous PbI2 is formed by incorporating small amount of rationally chosen additives into the PbI2 precursor solutions, which significantly facilitate the conversion of perovskite without any PbI2 residue. On the other hand, by employing a relatively high CH3NH3I concentration, a firmly crystallized and uniform CH3NH3PbI3 film is formed. As a result, a promising power conversion efficiency of 16.21% is achieved in planar-heterojunction PVSCs. Furthermore, it is experimentally demonstrated that the PbI2 residue in perovskite film has a negative effect on the long-term stability of devices.