Tin dioxide (SnO2), an n-type semiconductor, is widely studied due to its applicability in solar cells, sensors, and energy storage devices. In particular, SnO2 has garnered considerable interest as an anode material for Li-ion batteries due to its high theoretical capacity of 1494 mAh/g and affordability. Lithiation in SnO2-based anodes entails conversion and alloying reactions. SnO2 first irreversibly reacts with lithium ions to form Sn and Li2O, resulting in substantial capacity loss. Thereafter, Sn reacts with Li through reversible alloying, which leads to large volume expansion, pulverization of the particles, and steady growth of the solid electrolyte interface. These issues collectively contribute to lower capacity retention and restrict cycling stability. Reducing the crystallite size is a suitable method of overcoming these limitations as it increases electronic conductivity, reduces lithium-ion diffusion length, and better handles volume variations. In this work, two various morphologies of SnO2 samples, i.e., SnO2-Faceted and SnO2-Spherical particles, were synthesized. This has been done by hydrothermal synthesis through polyvinylpyrrolidone (PVP) of different molecular weights, leading to different crystallite sizes and morphologies. These structural differences improve electrochemical performance by increasing the accessible active surface area and reducing the lithium-ion diffusion distance, resulting in increased specific capacity and improved cycling stability.