This study presents a comprehensive investigation of vanadium tetrasulfide (VS₄) cathodes for solid-state lithium batteries, utilizing innovative material characterization techniques, including time-of-flight secondary ion mass spectrometry (ToF-SIMS), Raman spectroscopy, scanning electron microscopy (SEM), and focused ion beam-SEM. The effects of milling intensity and solid electrolyte (SE) content on microstructural evolution and electrochemical performance are thoroughly examined. VS₄ composites are analyzed, revealing significant morphological and structural transformations. Notably, ToF-SIMS provides unprecedented insights into the lithiation process, highlighting the formation of lithium sulfide species and structural changes during cycling. Electrochemical testing demonstrates that high energy ball-milled composites exhibit superior discharge rate capability and cycling stability, achieving discharge capacities of up to 1466 mAh g_s⁻¹ at 0.05 C and 1150 mAh g_s⁻¹ at 1.00 C. The study emphasizes the critical role of SE content in enhancing lithium ion conductivity and interfacial contact, contributing to improved electrochemical performance. Furthermore, the development of a scalable dry-film processing method is explored, showcasing its potential for high power density applications. Overall, this research underscores the viability of VS₄ as a promising cathode material for fast charging solid-state batteries, paving the way for advanced sulfur-based energy storage technologies.