Layer-by-layer (LbL) capsules, known for their versatility and smart response to environmental stimuli, have attracted great interest in drug delivery applications. However, achieving a desired drug delivery system with sustained and tunable drug release is still challenging. Here, a thermoresponsive drug delivery system of solid dexamethasone nanoparticles (DXM NPs, 200 +/- 100 nm) encapsulated in a model LbL assembly of tunable thickness consisting of strong polyelectrolytes poly(diallyldimethylammonium chloride)/poly(styrenesulfonate) (PDAC/PSS) is constructed. The influence of various parameters on drug release, such as number of layers, ionic strength of the adsorption solution, temperature, and outermost layer, is investigated. Increasing the number of layers results in a thicker encapsulating nanoshell and decreases the rate of dexamethasone release. LbL assemblies created in the absence of salt are most responsive to temperature, yielding the greatest contrast in drug release. Relationships between drug release and LbL architecture are attributed to the size and concentration of free volume cavities within the assemblies. By tailoring the properties of those cavities, a thermoresponsive drug delivery system may be obtained. This work provides a promising example of how LbL assemblies may be implemented as temperature-gated materials for the controlled release of drug, thus providing an alternative approach to the delivery of therapeutics with reduced toxic effects.