We investigate the effects of temperature and reaction time on structural, morphological, and optical properties of BaMoO4 and BaWO4 synthesized via precipitation induced by a fast precursor injection. Oriented aggregation and matter transfer influenced the particle sizes and shapes. The morphological changes were responsible for manipulating the maximum photoluminescence (PL) emissions from blue to red, exclusively in BaWO4. The broadband PL profiles and band gap energies (from 4.08 to 4.98 eV) suggested the participation of direct electronic transitions among intermediary energy levels in the forbidden region. The proposed template/surfactant-free approach has the potential to growth hierarchical structures of tungstates/molybdates with improved optical properties.