Titanium oxyfluoride TiOF2 finds a wide range of applications in photocatalytic processes, pigments, lithium ion batteries, etc. The present work proposes a novel, simple and productive TiOF2 synthesis route through hydrolysis of the titanium fluoride solution. It was demonstrated that the process resulted with the formation of two polymorph modifications, hexagonal h-TiOF2 (space group ̅) and cubic с-TiOF2 (space group ̅). It was found that the proportion between the resulting phases is dependent on synthesis conditions. In particular, the presence of hydrogen peroxide during titanium tetrafluoride hydrolysis provided formation of exclusively cubic TiOF2 phase. Moreover, the correlation between calcination temperature and phase composition of the synthesized titanium oxyfluoride samples was found. Band gap Eg was determined for the samples consisting of с-TiOF2 phase only, as well as for the mixture of both hexagonal and cubic modifications.