Triarylamine (TAA) and related materials have dramatically promoted the development of organic and hybrid photovoltaics during the past decade. The power conversion efficiencies of TAA-based organic solar cells (OSCs), dye-sensitized solar cells (DSSCs), and perovskite solar cells (PSCs) have exceeded 11%, 14%, and 20%, which are among the best results for these three kinds of devices, respectively. In this review, we summarize the recent advances of the high-performance TAA-based materials in OSCs, DSSCs, and PSCs. We focus our discussion on the structure-property relationship of the TAA-based materials in order to shed light on the solutions to the challenges in the field of organic and hybrid photovoltaics. Some design strategies for improving the materials and device performance and possible research directions in the near future are also proposed.

A linear solution‐processable small molecule (BDT‐2DPP) based on 5‐alkylthiophene‐2‐yl‐substituted benzodithiophene and diketopyrrolopyrrole is designed and synthesized. BDT‐2DPP exhibits strong and broad absorption with low band gap, low lying energy levels matching with PC61BM and high hole mobility. Solution‐processed organic solar cells based on BDT‐2DPP:PC61BM blend showed power conversion efficiencies as high as 5.79%.