Triarylamine derivatives containing electron donating methoxy units provide outstanding device performance as dopant-free hole transporting materials in inverse type planar heterojunction perovskite solar cells.

P‐Type redox‐active organic materials (ROMs) draw increasing attention as a promising alternative to conventional inorganic electrode materials in secondary batteries due to high redox voltage, fast rate capability, environment friendliness, and abundance. First, fundamental properties of the p‐type ROMs regarding the energy levels and the anion‐related chemistry are briefly introduced. Then, the development progress of the p‐type ROMs is outlined in this review by classifying them according to their redox centers. The molecular design strategies employed for improving their electrochemical performance are discussed to guide further research. Finally, a summary of the electrochemical performance achieved, regarding voltage, specific energy with power, and cycle stability, is provided with perspectives.