Successful exploitation of semiconductor nanocrystals (NCs) in commercial products is due to the remarkable progress in the wet-chemical synthesis and controlled assembly of NCs. Central to the cadence of this progress is the ability to understand how NC growth and assembly can be controlled kinetically and thermodynamically. The arrested precipitation strategy offers a wide opportunity for materials selection, size uniformity, and morphology control. In this colloidal approach, capping ligands play an instrumental role in determining growth parameters and inter-NC interactions. The impetus for exquisite control over the size and shape of NCs and orientation of NCs in an ensemble has called for the use of two or more types of ligands in the system. In multiple ligand approaches, ligands with different functionalities confer extended tunability, hinting at the possibility of atomic-precision growth and long-range ordering of desired superlattices. Here, we highlight the progress in understanding the roles of ligands in size and shape control and assembly of NCs. We discuss the implication of the advances in the context of optoelectronic applications.