Atomic layer deposition (ALD) has become an indispensable thin-film technology in the contemporary microelectronics industry. The unique self-limited layer-by-layer growth feature of ALD has outstood this technology to deposit highly uniform conformal pinhole-free thin films with angstrom-level thickness control, particularly on 3D topologies. Over the years, the ALD technology has enabled not only the successful downscaling of the microelectronic devices but also numerous novel 3D device structures. As ALD is essentially a variant of chemical vapor deposition, a comprehensive understanding of the involved chemistry is of crucial importance to further develop and utilize this technology. To this end, we, in this review, focus on the surface chemistry and precursor chemistry aspects of ALD. We first review the surface chemistry of the gas–solid ALD reactions and elaborately discuss the associated mechanisms for the film growth; then, we review the ALD precursor chemistry by comparatively discussing the precursors that have been commonly used in the ALD processes; and finally, we selectively present a few newly-emerged applications of ALD in microelectronics, followed by our perspective on the future of the ALD technology.