© 2020 by the authors. Licensee MDPI, Basel, Switzerland. In this study, a dual-phase Li4Ti5O12-TiO2 microrod was successfully prepared using a modified hydrothermal method and calcination process. The stoichiometry of LiOH as precursor was varied at mol ratio of 0.9, 1.1, and 1.3, to obtain the appropriate phase composition between TiO2 and Li4Ti5O12. Results show that TiO2 content has an important role in increasing the specific capacity of electrodes. The refinement of X-ray diffraction patterns by Rietveld analysis confirm that increasing the LiOH stoichiometry suppresses the TiO2 phase. In the scanning electron microscopy images, the microrod morphology was formed after calcination with diameter sizes ranging from 142.34 to 260.62 nm and microrod lengths ranging from 5.03–7.37 μm. The 0.9 LiOH sample shows a prominent electrochemical performance with the largest specific capacity of 162.72 mAh/g and 98.75% retention capacity achieved at a rate capability test of 1 C. This finding can be attributed to the appropriate amount of TiO2 that induced the smaller crystallite size, and lower charge transfer resistance, enhancing the lithium-ion insertion/extraction process and faster diffusion kinetics.