This work presents the benefits of the superlattice approach to control light emission properties of materials with Si nanoclusters and rare-earth ions. The undoped and Nd3+-doped both Si-rich-SiO2 single layers and Si-rich-SiO2/SiO2 superlattices were grown by radio frequency magnetron sputtering. Their properties were investigated by means of spectroscopic ellipsometry, Fourier infrared transmission spectroscopy, transmission electron microscopy, and photoluminescence (PL) methods versus deposition conditions, annealing treatment, and superlattice design (doping and thickness of alternated sublayers). An intense Nd3+ emission from as-deposited single layers and superlattices was observed. The lower annealing temperature (below 900 °C) of the single layers and superlattices favors the formation of amorphous Si clusters that act as effective sensitizers of rare-earth ions. The highest Nd3+ PL intensity was achieved after a conventional annealing at about 600–800 °C in nitrogen flow for all samples. Crystallized Si-nanoclusters were formed in Si-rich-SiO2 single layers upon annealing at 1000–1100 °C, whereas their formation in the superlattices occurred at higher temperatures (1100–1150 °C). The mechanism of Nd ions' excitation via energy transfer from Si-nanoclusters and/or matrix defects, if any, is discussed.