TiO(B) is a promising anode material for lithium-ion batteries (LIBs) due to its fast lithiation/delithiation kinetics, however, its thermodynamic metastable nature makes it difficult to synthesize pure phase, which significantly affects its lithium storage capability. Herein, the structural evolution from precursor to TiO(B) is systematically investigated and it is revealed that the formation of high-purity monoclinic HTO (hydrogen titanate) precursor is the key to preparing TiO(B) with high purity, which can be achieved via tailored-design the solvent structures of Ti in the precursor solution. Glycolic acid (GA) is favorable for the synthesis of high-purity HTO, benefiting from its simplest spatial structure and coplanar carboxyl and hydroxyl groups for Ti coordination, further leading to the formation of TiO(B) with a high phase purity of 98.83% that exhibits excellent rate capability (80.5% capacity retention with current densities increased from 1 to 30 C), thus making it a promising candidate for simultaneous energy and power density LIBs anode.