This study investigates the phase and elemental distribution in a suspension plasma-sprayed (SPS) Li4Ti5O12 (LTO) thin-film anode for solid-state lithium batteries, deposited on an SS-304 substrate. Advanced synchrotron-based µXRD and µXRF techniques were employed for micro-scale characterization, revealing distinct phase regions influenced by thermal exposure during the SPS process. The dominant Li4Ti5O12 phase was retained across most of the film, with localized transformations to secondary phases Li2Ti3O7, Li2TiO3, and TiO2 near the substrate interface, primarily due to prolonged high-temperature exposure and subsequent lithium loss. These findings underscore the importance of controlling SPS parameters to minimize lithium loss and optimize phase stability and interfacial integrity in solid-state battery components.