We present a low-temperature, hydrothermal synthesis method for Ta-doped TiO2. Here, alkoxide-based precursors are mixed at low temperatures to suppress differential hydrolysis and phase separation. This method ensures homogeneous, molecular mixing of the Ta dopant with the native oxide up to a concentration of ∼2.5 at.%. X-ray diffraction and energy dispersive spectrometer analyses confirm a uniformly doped rutile TiO2. Scanning electron microscopy and transmission electron microscopy analyses reveal a highly branched structure. Optoelectronic properties of these structures were investigated using ultraviolet-visible spectroscopy and low-temperature photoluminescence.