This work reports the synthesis of titanium oxide (TiO2) in anatase and rutile phases prepared by the polymeric precursors method. The synthesis was investigated in function of the precursors’ molar ratios and calcination temperature, in long treatment times. The characterization revealed the complete retention of anatase phase in high organic:metal molar ratios. From surface area measurements, this work evidences the existence of a critical size for anatase stabilization, as observed in previous works.