The reaction between (NH4)2TiF6 and H3BO3 in the presence of varying quantities of PEG-6000 was used to form NH4TiOF3 mesocrystals (MCs). The amount of PEG-6000, employed as a template, is crucial to the formation of defect free, non-agglomerated NH4TiOF3 MCs; high concentrations lead to MC agglomeration, lower ones result in centralized defects. This polymer-mediated formation process may be understood using an analogy with known polymerization reactions. The oxofluorotitanate MCs readily undergo a thermal topotactic transformation to give anatase MCs with photocatalytic activity. The TiO2 MCs are porous, with highly orientated lamellar crystallites that form part of the larger mesocrystal structure.