Cerium and chromium co-doped gadolinium aluminum gallium garnets were prepared using sol-gel technique. These compounds potentially can be applied for NIR-LED construction, horticulture and theranostics. Additionally, magnesium and calcium ions were also incorporated into the structure. X-ray diffraction data analysis confirmed the all-cubic symmetry with an Ia-3d space group, which is appropriate for garnet-type materials. From the characterization of the luminescence properties, it was confirmed that both chromium and cerium emissions could be incorporated. Cerium luminescence was detected under 450 nm excitation, while for chromium emission, 270 nm excitation was used. The emission of chromium ions was exceptionally intense, although it was determined that these compounds are doped only by parts per million of Cr3+ ions. Typically, the emission maxima of chromium ions are located around 650–750 nm in garnet systems. However, in this case, the emission maximum for chromium is measured to be around 790 nm, caused by re-absorption of Cr3+ ions. The main observation of this study is that the switchable emission wavelength in a compound of single phase was obtained, despite the fact that doping with Cr ions was performed in ppm level, causing an intense emission in NIR region.