Colloidal nanocrystals (NCs) are intriguing building blocks for assembling various functional thin films and devices. The electronic, optoelectronic, and thermoelectric applications of solution-processed, inorganic ligand (IL)-capped colloidal NCs are especially promising as the performance of related devices can substantially outperform their organic ligand-capped counterparts. This in turn highlights the significance of preparing IL-capped NC dispersions. The replacement of initial bulky and insulating ligands capped on NCs with short and conductive inorganic ones is a critical step in solution-phase ligand exchange for preparing IL-capped NCs. Solution-phase ligand exchange is extremely appealing due to the highly concentrated NC inks with completed ligand exchange and homogeneous ligand coverage on the NC surface. In this review, the state-of-the-art of IL-capped NCs derived from solution-phase inorganic ligand exchange (SPILE) reactions are comprehensively reviewed. First, a general overview of the development and recent advancements of the synthesis of IL-capped colloidal NCs, mechanisms of SPILE, elementary reaction principles, surface chemistry, and advanced characterizations is provided. Second, a series of important factors in the SPILE process are offered, followed by an illustration of how properties of NC dispersions evolve after ILE. Third, surface modifications of perovskite NCs with use of inorganic reagents are overviewed. They are necessary because perovskite NCs cannot withstand polar solvents or undergo SPILE due to their soft ionic nature. Fourth, an overview of the research progresses in utilizing IL-capped NCs for a wide range of applications is presented, including NC synthesis, NC solid and film fabrication techniques, field effect transistors, photodetectors, photovoltaic devices, thermoelectric, and photoelectrocatalytic materials. Finally, the review concludes by outlining the remaining challenges in this field and proposing promising directions to further promote the development of IL-capped NCs in practical application in the future.