The heterointerfaces of charge-selective contacts are crucial in determining efficiency and stability of perovskite optoelectronic devices, where the fundamental knowledge of the buried heterointerface between perovskite and bottom charge transport layer is less well understood compared to the top interface. Herein, we systematically investigate the energetics at the perovskite/SnO2 buried heterointerface for an n-i-p perovskite solar cell (PSC) and the perovskite/PEDOT:PSS buried heterointerface for a p-i-n one, respectively. In contrast to previous cognitions, we discover a perovskite transition phase at the buried interface region that originates from the chemical bonding interaction with the bottom charge transport layer. The transition phase causes an energy level barrier and induces defects, impeding charge transport across the heterointerface. These detrimental effects trigger significant nonradiative recombination and limit the attainable device photovoltage. We then develop the energetic models that describe such buried heterointerfaces. Moreover, we further test the proposed model -derived mechanisms via inserting a thin polyvinyl alcohol layer into the buried heterointerfaces of the de-vices. We demonstrate that chemical interactions and formation of the perovskite transition phase at the buried heterointerface thereby are fully restrained, leading to a diminished electron extraction barrier and improved charge transport. As a result, significant increases in open-circuit voltage and fill factor of the devices are ach-ieved. These results will help guide future efforts on developing suitable buried heterointerfaces for superior performance of perovskite optoelectronics.