ConspectusThe widespread use of electrical plants and grids to generate, transmit, and deliver power to consumers makes electricity the most convenient form of energy to transport, control, and use. Balancing electricity demand with electricity supply requires a mechanism for energy storage, which is enabled by electrical energy storage devices such as batteries and supercapacitors. In addition to the grid-level energy storage, we have all witnessed the quick growth of a number of applications that require autonomous power, illustrated by the Internet of Things, and electrification of transport. Batteries, when developed for targeted applications with specific requirements, require new materials with improved performance enabled by rational design on the atomic level. The material tunability knobs include chemical composition, structure, morphology, and heterointerfaces, among others. Synthesis methods that could enable control of these parameters while offering versatility and being facile are highly desired.In this Account, we describe a synthesis strategy for the creation of new intercalation host oxides, hybrid materials, and compounds with oxide/carbon heterointerfaces for use as electrodes in intercalation batteries. We begin by introducing a strategy called the chemical preintercalation synthesis approach and describing processing steps that can be used to tune the material's chemical composition, structure, and morphology. We then show how the chemical preintercalation of inorganic ions can be used to improve the ion diffusion and stability of the synthesized materials. We reveal how confined interlayer water can be controlled and how the degree of hydration affects the electrochemical performance. This is followed by a demonstration of the chemical preintercalation of organic molecules leading to unprecedented expansion of the interlayer region up to ∼30 Å and initial electrochemical characterization of the obtained hybrid materials. We then present evidence that the carbonization of the interlayer organic molecules is an efficient synthetic pathway for creating oxide/carbon heterointerfaces and improving the electronic conductivity of oxides, which leads to improved stability and rate capability during electrochemical cycling. The examples discussed in this Account show that the chemical preintercalation synthesis approach opens pathways for the preparation of materials that have not been synthesized previously, such as new phases, hybrid materials, and 2D heterostructures with advanced functionalities. We demonstrate that chemical preintercalation can be used to effectively tune the chemistry of the confined interlayer region in layered phases and form tight oxide/carbon heterointerfaces enabling control of the material properties at the atomic level.