A novel strategy was introduced to produce large-scale pristine MgO nanostructures as a feasible candidate for light harvesting applications. Herein, MgO nanostructures with a nanoflakes-/nanofibers-like morphology were synthesized by a co-precipitation route at different calcination temperatures ranging from 500 to 1100 degrees C and well characterized by several standard experimental techniques, such as XRD, FTIR, SEM, EDX, and TEM, to confirm the formation of MgO nanostructures. Undoped MgO nanostructures obtained at 1100 degrees C exhibited a strong photoluminescence (PL) emission spectrum at 668 nm (hypersensitive red) at 466 nm excitation wavelength. Moreover, these nanostructures also showed strong blue (477 nm) and red (668 nm) luminescence emissions simultaneously at an excitation wavelength of 317 nm. Further investigations probed by PL mapping demonstrated the homogeneous distribution of PL intensity throughout the MgO surfaces and time-resolved photoluminescence spectroscopy results of these nanostructures indicated a decay time of less than 10 ns. Thus, the facile synthesis of these luminescent undoped MgO nanostructures provides a potential platform to harvest white light generation (a combination of blue and red emissions) as well as their potential use in LED applications