The charge-selective contacts play a crucial role in the charge dynamics of solar cells. In the fast race to achieve higher power conversion efficiencies in perovskite-based devices, the avoidance of the detrimental effects due to interfacial charge recombination and/or poor charge extraction is the key to achieving high performance devices. The unique molecular structure of self-assembled molecules (SAMs) offers the possibility to tune the different parts of the molecule by precise design of its components to achieve desirable energy levels and molecular dipoles to facilitate the charge transfer. Therefore, the application of the SAMs as selective contacts emerges as a promising route to achieve high performance perovskite solar cells with the advantage of low material consumption, longer lifetimes and reduced interfacial non-radiative recombination. In this review, we summarize the recent literature about SAMs applied as selective hole or electron contacts. The objective of the present review is to unravel the open questions related to these molecules and propose our perspective about the development of SAMs for the development of cost-efficient and stable perovskite solar cells. In this review, we summarize the recent advances about self-assembled molecules (SAMs) applied as selective hole or electron contacts for perovskite solar cells.