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In less than three years, the photovoltaic community has witnessed a rapid emergence of a new class of solid‐state heterojunction solar cells based on solution‐processable organometal halide perovskite absorbers. The energy conversion efficiency of solid‐state perovskite solar cells (PSCs) has been quickly increased to a certified value of 20.1% by the end of 2014 because of their unique characteristics, such as a broad spectral absorption range, large absorption coefficient, high charge carrier mobility and diffusion length. Here, the focus is specifically on recent developments of hole‐transporting materials (HTMs) in PSCs, which are essential components for achieving high solar cell efficiencies. Some fundamentals with regard to PSCs are first presented, including the history of PSCs, device architectures and general operational principles of PSCs as well as various techniques developed for the fabrications of …