ZnGa2O4 and ZnGa2O4: Mn2+/Eu3+ with uniform nanosphere (diameter about 400 nm) morphology have been synthesized via a facile hydrothermal approach. XRD, Raman spectra, XPS, FT-IR, SEM, TEM, photoluminescence (PL), and cathodoluminescecne (CL) spectra are used to characterize the resulting samples. The controlled experiments indicate the dosage of trisodium citrate and pH values are responsible for shape determination of the ZnGa2O4 products. The possible fast crystallization-dissolution-recrystallization formation mechanism for these nanospheres is presented. Under UV light and low-voltage electron beam excitation, ZnGa2O4, ZnGa2O4: Mn2+ and ZnGa2O4: Eu3+ emit bright blue, green, and red luminescence, respectively. Based on density functional theory calculations from first principles, the green and red emission are caused by the Mn 3d and Eu 4f electronic structures, respectively. Besides, the dependence of the CL intensity on the calcination temperature and electrical conductivity of the samples is presented. The ZnGa2O4: Mn2+ nanospheres have a higher CL intensity than that of bulk samples under the same excitation condition. The realization of three primary colors from a single host material suggests that full color display based on ZnGa2O4 nanospheres might be achievable, showing that these materials have potential applications in lighting and display fields.