The unprecedented emergence of perovskite‐based solar cells (PSCs) has been accompanied by an intensive search of suitable materials for charge‐selective contacts. For the first time a hole‐transporting self‐assembled monolayer (SAM) as the dopant‐free hole‐selective contact in p–i–n PSCs is used and a power conversion efficiency of up to 17.8% with average fill factor close to 80% and undetectable parasitic absorption is demonstrated. SAM formation is achieved by simply immersing the substrate into a solution of a novel molecule V1036 that binds to the indium tin oxide surface due to its phosphonic anchoring group. The SAM and its modifications are further characterized by Fourier‐transform infrared and vibrational sum‐frequency generation spectroscopy. In addition, photoelectron spectroscopy in air is used for measuring the ionization potential of the studied SAMs. This novel approach is also suitable for achieving a conformal coverage of large‐area and/or textured substrates with minimal material consumption and can potentially be extended to serve as a model system for substrate‐based perovskite nucleation and passivation control. Further gains in efficiency can be expected upon SAM optimization by means of molecular and compositional engineering. A novel concept for the formation of the hole selective layer in efficient perovskite solar cells is presented. Carbazole‐based material is synthesized and used for the formation of a self‐assembled monolayer on top of the indium tin oxide transparent conductive substrate. Power conversion efficiency as high as 17.8% is achieved.