We synthesize the phosphor Na3HTi1-xMnxF8 (Na3HTiF8:Mn4+) material series using a coprecipitation method. We determine the complete phase and crystallographic structure of the Na3HTiF8 series end-member, including the determination of the H atoms at the 4b (0, 1/2, 0) crystallographic site within the Cmcm space group symmetry structure, resulting in a quantum efficiency of ∼44%, which is comparative to the Na2SiF6:Mn4+ phosphor materials. We successfully model the luminescent properties of the Na3HTi1-xMnxF8 material series, including temperature and time-dependent photoluminescence, providing a good prediction of the decay properties at low and high temperature and revealing the existence of Mn5+ during the ionization process. Notably, LED package data indicates that the Na3HTi1-xMnxF8 material series could be a promising candidate for high-level and back-lighting devices. This research reveals the role that hydrogen plays in determining fluoride phosphor structure and properties, revealing a new path for the synthesis of fluoride phosphors.