Controlling luminescence in phosphors able to produce several emissions from different stable excited states determines their use in optical devices. We investigate the color control mechanism that quenches the greenish-blue emission in favor of the red one in the archetype phosphor CaTiO3:Pr3+. State-of-the-art ab initio calculations indicate that direct host-to-dopant energy transfer (released by electron-hole recombination following the interband excitation and structural reorganization) selectively populates the 1D2 red luminescent state of Pr3+ and bypasses the 3P0 greenish-blue emitter. Local defects can modulate the electron-hole recombination energy and therefore increase the red emission efficiency, as experimentally observed. The selection of red emission does not happen in CaZrO3:Pr3+ because the electron-hole recombination energy is much higher. The calculations could not support the widely accepted color control mechanism based on metal-to-metal charge transfer states. The conclusion sets new points of view for the color control of lanthanide activated inorganic phosphors.