Metal‐halide perovskites offer great potential to realize low‐cost and flexible next‐generation solar cells. Low‐temperature‐processed organic hole‐transporting layers play an important role in advancing device efficiencies and stabilities. Inexpensive and stable hole‐transporting materials (HTMs) are highly desirable toward the scaling up of perovskite solar cells (PSCs). Here, a new group of aniline‐based enamine HTMs obtained via a one‐step synthesis procedure is reported, without using a transition metal catalyst, from very common and inexpensive aniline precursors. This results in a material cost reduction to less than 1/5 of that for the archetypal spiro‐OMeTAD. PSCs using an enamine V1091 HTM exhibit a champion power conversion efficiency of over 20%. Importantly, the unsealed devices with V1091 retain 96% of their original efficiency after storage in ambient air, with a relative humidity of 45% for over 800 h, while the devices fabricated using spiro‐OMeTAD dropped down to 42% of their original efficiency after aging. Additionally, these materials can be processed via both solution and vacuum processes, which is believed to open up new possibilities for interlayers used in large‐area all perovskite tandem cells, as well as many other optoelectronic device applications. A new group of aniline‐based enamine hole‐transporting materials is synthesized, characterized, and tested in perovskite solar cells, yielding a champion power conversion efficiency over 20%. The investigated materials are obtained via one‐step synthesis procedure, without the use of a transition metal catalyst, from a very common and inexpensive precursor—aniline.