Li1.1V3O8 (LVO) has shown promise as a cathode material for lithium-based batteries due to its high theoretical capacity (360 mAh.g(-1)) and good rate capability; however, LVO batteries suffer from capacity fade upon extended cycling. The impact of synthetic material control on electrochemistry and capacity retention was explored through solvothermal synthesis of LVO fibers and sol-gel synthesis of LVO rhombohedrons. Cyclic voltammetry (CV) of the twomaterials revealed key differences where lithiation of the solvothermal-derived LVO material resulted in less beta phase formation as compared with the sol-gel-derived material. Structural evolution of the materials during lithiation was characterized through in situ XRD which revealed that the alpha ->beta phase conversion is essentially complete in the sol-gel product with only partial conversion in the solvothermal product. Under galvanostatic cycling, the sol-gel product delivered higher capacity but displayed more capacity fade as compared to the solvothermal product as foretold by both CV and XRD findings. When cycled within the a phase region, improved preservation of both energy delivery and structural integrity was observed. These findings substantiate the proposed cause of capacity degradation as originating from an alpha ->beta structural change and illustrate the possibility of minimizing alpha ->beta phase formation through synthetic control of LVO. (C) 2019 The Electrochemical Society.