the majority of the market shares as compared to next-generation thin-film PV technologies. Nevertheless, technological challenges in improving efficiencies and decreasing the high-energy requirements connected to the fabrication of silicon PV results in a higher global warming potential. In an effort to achieve lower fabrication cost and higher efficiencies, different types of thin-film PV technologies have been developed including dyesensitized solar cells, [2,3] organic solar cells, [4,5] copper indium tin sulfur [6,7] and emerging organic-inorganic lead halide perovskite solar cells (PSCs). [8,9] The combined merits of low fabrication cost and high power conversion efficiency (PCE) are distinct features of PSCs where PCE has jumped from 3.8% [8] to 25.2% [10] in just a decade. Such a sharp increase in PCE is mainly attributed to the large absorption coefficient, [11] long carrier lifetime, [12] high trap resistance, [13] high dielectric constant, [14-16] low binding energy, [17] and tunable bandgap of 1.2−1.7 eV, [18] all combined in a single perovskite material. 1.1. Perovskite Solar Cell Device Structures A typical perovskite solar cell consists of a light-absorbing perovskite layer which is sandwiched between an electron transport layer (ETL) and a hole transport layers (HTL). To complete the device, ETL is supported on a transparent conducting oxide (TCO) front electrode, and HTL on metal-coated back contact electrode, Figure 1. There are two basic structures for the PSC: the so-called mesoporous structure, which contains a mesoporous ETL layer (i.e., mesoporous TiO 2), and the planar structure, as depicted in Figure 1a,b. Even though early reports based on mesoporous devices assumed that the perovskite infiltration through the mesoporous scaffold improved the charge carrier collection to the electrode, later investigations performed by Lee and co-workers replaced the TiO 2 with an insulating Al 2 O 3 mesoporous layer, and reported for the first time the ambipolar nature of the perovskite materials, allowing the realization of longer diffusion length. [19] This enabled the fabrication of planar devices, and gave rise to an impressive evolution of device architectures, novel materials and cell configurations either in n-i-p or p-in designs. [12,19,20] In addition, Due to a certified 25.2% high efficiency, low cost, and easy fabrication; perovskite solar cells (PSCs) are the focus of interest among the nextgeneration photovoltaic technologies. Long-term stability is one of the most challenging obstacles to bring technology from the lab to the market. In this review, applications of self-assembled monolayers (SAMs) to enhance the power conversion efficiency (PCE) and stability of PSCs is discussed. In the first part, the introduction of SAMs, and deposition techniques applied to different PSC architectures are described. In the middle section, current efforts to utilize SAMs to fine-tune the optoelectronic properties to enhance the PCE and stability are detailed. The improvements in surface morphology, energ...