The crystal structure of perovskite has a significant influence on the photovoltaic performance and stability of perovskite solar cells (PSCs). Pb4+ is introduced into CH3NH3PbI3 (MAPbI(3))-based PSCs by participating the octahedral [PbI6](4-) structure, then to induce the formation of stronger Pb-I bond and reduce [PbI6](4-) octahedron distortion, which would improve structural symmetry, decrease the degree of disorder and be beneficial to the crystallization of perovskites. Synchrotron based X-ray absorption fine spectroscope (XAFS) revealed that the existence of higher valence state lead could be realized by doping Pb4+ directly or induced by electron withdrawing group, in consequence the [PbI6](4-) octahedral structure becomes more stable. Grazing incidence X-ray diffraction (GIXRD) especially demonstrates that Pb4+ with appropriate proportion may well replace part of Pb2+ to form an uniform phase in the primal perovskite structure to improve the crystallization on the surface and homogeneous out-of-plane (OOP) ordered crystal accumulation in the bulk, which is also important for improving the efficiency and stability of PSCs. As a result, a power conversion efficiency (PCE) exhibits a 42.1% increase with the doping of 0.03% PbF4 and 0.075% PCBM compared with a pristine device and its stability improves markedly after 30 days of storage in ambient atmosphere.