Since the lithium-ion diffusion pathways in LiFePO₄OH are highly anisotropic with lithium-ion migration in tunnels running along the c-axis in its 3D framework, controlled morphology with preferential orientation is vital for enhanced electrochemical rate performance. Herein, we focus on synthesizing cost-effective and environmentally benign tavorite structured LiFePO₄OH hydroxyphosphate via a low-temperature (solvo)hydrothermal approach. To get insights into the role of solvent on the morphology and electrochemical performance of tavorite compound, various combination of water and ethylene glycol has been employed as solvent medium for the synthesis of polycrystalline LiFePO₄OH. SEM images of all samples revealed uniform micrometric particles with rods/platelets-like morphology. We observed that the preferential orientation of crystallographic facets along specific planes stipulates enhanced rate capability combined with good electrochemical performance. The biphasic nature of lithium (de)insertion led to the formation of an amorphous Li₂FePO₄OH upon first discharge, which was further probed by combining ex-situ and in-situ spectroscopy, structural, microscopy, and electrochemical techniques.1–4 When cycled in different voltage ranges, i.e.,1.5-4.2 V, 2.0-3.2 V, 1.5-4.5 V vs. Li⁺/Li, the electrochemical and structural mechanism of LiFePO₄OH was investigated through electrochemical titration tools, impedance spectroscopy, and ex-situ diffraction. The galvanostatic cycling performance of hydrothermal and solvothermal synthesized LiFePO₄OH materials showed facile Li+ (de)intercalation with an Fe⁺³/Fe⁺² redox potential ~2.5-2.6 V (vs. Li⁺/Li) in the potential window of 2.2-4.2 V. We have observed the highest discharge capacity of 140 mAh g^-1 with good capacity retention and excellent reversibility registering 99% coulombic efficiency upto 60 cycles. The enhanced activity can be attributed to the synergistic effect of particle downsizing and intimate carbon coating on the particle surface through mechanical milling. The structure, magnetic and electrochemical properties of LiFePO₄OH will be revisited.