Perovskite solar cells (PSCs) are remarkably efficient. Recent years have witnessed a surge in PSC researches in both material development and structure optimization. In a PSC, a lead halide perovskite absorber is typically sandwiched between layers of hole and electron transport materials (i.e., HTM and ETM, respectively) to facilitate the extraction of photoexcited charges, but this may also create issues of energy level mismatch and interfacial degradation. A critical challenge for both HTM and ETM materials is the ineffective charge collection because of their incompatible work functions with the perovskite, which causes significant efficiency loss. In addition, the electron mobility of an ETM doesn’t typically match with the hole mobility in an HTM, leading to interfacial charge accumulation, hysteresis and degradation. There have been extensive efforts in developing materials via work-function modulation and interfacial treatment; however, they are expensive and challenging, and may not be compatible with the solution processing of the perovskite. In this work, we demonstrated replacing HTM and ETM with two pairs of nonaqueous redox couples to extract charges from the perovskite-electrolyte interfaces through photoelectrochemical or electrochemical reactions. These redox couples, dissolved in a low dielectric constant solvent, are not only to fully encapsulate and stabilize the perovskite, but also offer easy fine-tuning of their electrochemical properties to match with the perovskite. Most importantly, the nonaqueous redox couples serve as efficient energy media and solar energy can be directly converted/stored into chemical energy at the point of solar energy generation without the intermediate step such as electricity. Recent progress will be discussed and the intricate interplay between the perovskite layer morphology and redox couples will be presented.