Automated spray-layer-by-layer (LbL) assembly was used to create highly reflective structurally colored thin films with high reflectance at near-UV light wavelengths. Reflectance peaks were tuned by fabricating alternating stacks of high (TiO(2) nanoparticles) and low (SiO(2) nanoparticles) refractive index materials using a non-quarter-wave design. Spray-assembled multilayer heterostructures fabricated with up to 840 individual polymer or nanoparticle deposition steps presented similar roughness and refractive index values compared to Bragg stacks obtained via immersion LbL assembly. Such complex multilayer heterostructures, however, could be fabricated in significantly shorter times; the time required to deposit a complete bilayer was only about 90 s, compared to 36 min for the immersion assembly of the same system. Optimization of the experimental parameters was performed to achieve uniform coatings and relatively smooth interfaces and surfaces. We observed that the spraying times of the nanoparticle and polymer solutions are the main parameters that determine the thickness, optical properties, and uniformity of the assembled films. Ellipsometry, atomic force microscopy (AFM), UV-vis spectroscopy, and transmission electron microscopy (TEM) were used to characterize the samples. The nanoparticle thin films were iridescent and presented relatively narrow peaks of high reflectance (similar to 90%) at visible and near-UV wavelengths of light.