<p>Droplet microfluidic technology is an emerging technique that enables the precise manipulation of microdroplets and has attracted considerable attention since its development. It exhibits broad application prospects in the field of energetic materials. In this study, spherical nanothermites with regular morphologies (n-Al/Fe₂O₃, n-Al/CuO, n-Al/MoO₃, and n-Al/MnO₂) were prepared using a coaxial droplet microfluidic platform. The samples were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and high-speed photography to analyze their morphology, structure, composition, thermal properties, combustion behavior, and calorific value. The results showed that the thermite microspheres prepared by droplet microfluidization possessed regular morphologies, good dispersion, and uniform particle sizes. DSC analysis revealed two exothermic peaks associated with the thermite reaction and one endothermic peak corresponding to the melting of aluminum powder, except for n-Al/Fe₂O₃, which exhibited an additional endothermic peak at approximately 530°C. Combustion experiments demonstrated that the microspheres exhibited excellent and stable combustion performance. Among the samples, n-Al/MoO₃ exhibited the fastest burning rate and the brightest flame, whereas n-Al/Fe₂O₃ showed the slowest combustion rate and more dispersed flame characteristics. n-Al/CuO and n-Al/MnO₂ displayed similar combustion behaviors, although n-Al/MnO₂ exhibited a slightly longer and brighter combustion process. Calorimetric measurements revealed that the spherical structuring of nano-aluminum thermites enhanced their energy-release efficiency. These findings indicate that droplet microfluidic technology can precisely control microdroplet morphology, thereby providing a useful strategy for the design and preparation of other advanced composite materials.</p>