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The manufacturing of three-dimensional colloidal structures on solid substrates is an important topic of applied research, aiming for photonic components especially in photovoltaic and sensor applications. Whereas conventional techniques such as wet self-assembly are based on engineering of the substrate surface energy, alternative strategies envisage the independence of the interfacial conditions. We report on inkjet printing of colloidal suspensions of monodisperse silica or polystyrene nanoparticles or both and their self-assembly to spherical colloidal photonic crystals. The formation process of the colloidal nanoparticles into stable spherical colloidal assemblies (SCAs) is achieved by a self-assembly process inside tiny droplets of a stochastic mist generated intentionally instead of a jet of individual single droplets using inkjet printing. The mist-jetted, shrinking droplets serve as confined geometries for the solidification of the nanoparticles during the evaporation; thus the particles are packed into stable ball-shaped assemblies. We show how fine-tuning of the jetting parameters allows the reliable generation and deposition of three-dimensional (3D) spherical colloidal assemblies of nanoparticles variable in size and with a high packing order. Microreflectance spectroscopy proves that the degree of order in the SCA is such that photonic stop bands occur inherent for photonic crystals.