Graphite/SiC (GSC) thin films were synthesized on silicon substrates via a spray method, depositing a Si-graphite solution on preheated silicon samples at 350 °C, followed by annealing at 800 °C for 4 h. A systematic approach was employed to ensure the effective incorporation of graphite into the SiC material during solution preparation. Various analytical techniques, including XPS, UPS, Reflection Energy Electron Loss Spectroscopy (REELS), PL, AFM, and Hall effect measurements, were employed for comparative analysis of the chemical composition, morphological, electrical, and optoelectronic properties of as-deposited and annealed GSC films. XPS analysis revealed the presence of Si—C and graphitic bonds in the as-deposited GSC, with a significant compositional shift to oxygen-rich graphite oxide/oxycarbides after annealing. REELS demonstrated increased bandgap and bulk plasmon energy due to surface oxidation, while UPS highlighted a high electronic density in the as-deposited film, diminishing after annealing. AFM revealed a tendency of as-deposited GSC grains to form smaller, sharper structures after annealing, resulting in smoother and more homogeneous surface morphology. Phase AFM confirmed graphite incorporation at grain boundaries and within the bulk, forming a composite structure. PL spectra of the as-deposited film exhibited a broad visible emission with distinct sub-peaks linked to SiC bandgap transitions and carbon-rich defects. Chromaticity diagrams indicated suitability for white LED applications. Hall effect measurements showed excellent electrical properties of the as-deposited GSC film, with high carrier density and mobility, which reduced significantly after annealing, transitioning the material to a more insulating state. These findings collectively provide a comprehensive understanding of GSC thin films’ properties and their potential applications.