The controlled regulation of A-site in rare earth manganate perovskites can orderly arrange the electronic states, leading to the emergence of unique transport properties. However, it is challenging to balance crystal structure stability and property variations during the multi-ion doping. In this study, a series of multivalent manganate perovskites are synthesized by hydrothermal method through the A-site multielement doping, which enables the manganese atoms with varying valence states to orderly arrange at the B site. Powder X-ray diffraction (PXRD) and X-ray absorption spectra (XAS) confirm that the splitting of the K─O hybrid orbitals in the crystal effectively prevents any distortion of the MnO