The direct conversion of solar energy into hydrogen through photoelectrochemical (PEC) cells has emerged as one of the most promising strategies for decarbonizing the energy sector, as it integrates into a single device photon harvesting, charge separation, and the hydrogen/oxygen evolution reactions. However, the overall efficiency of these systems remains limited by factors such as low spectral absorption, rapid electron-hole recombination, and structural instability of the photoelectrodes. In this context, the present work systematically mapped the relationships between processing conditions, structural features, and the resulting properties of two earth-abundant semiconductors: sub-stoichiometric tungsten oxide (WO???) and graphitic carbon nitride (g-C?N?), aiming at the future development of Z-scheme photoelectrodes for solar hydrogen production. WO??? films were deposited by reactive sputtering with O? flow gradients (2-10 sccm) and through the Reactive Gas Pulsing Process (RGPP) with duty cycles of 60% and 90% of the period. Characterization by X-ray Diffraction (XRD), Raman spectroscopy, Scanning Electron Microscopy (SEM), Electrochemical Impedance Spectroscopy (EIS), cyclic voltammetry, and Mott-Schottky analyses demonstrated that, although all samples exhibited the ?-monoclinic phase of WO???, those obtained with intermediate O? flows (6-8 sccm) showed superior photoelectrochemical performance, including lower charge transfer resistance, higher capacitance, energy density, and photocurrent under AM 1.5 G illumination. In the RGPP process, a 90% duty cycle led to the formation of transparent columnar films, while a 60% duty cycle produced denser and more reductive layers. These samples were thermally treated in both ambient air and flowing argon, revealing that the annealing atmosphere significantly influenced their optical transmittance and band gap variations. Upon annealing, sodium-containing glass substrates promoted the formation of Na?WO?, whereas Fluorine-doped Tin Oxide (FTO) substrates acted as ionic diffusion barriers, preserving the pure WO? phase. g-C?N? powders were obtained by thermal polycondensation of melamine between 400?°C and 550?°C. Only calcination at 550?°C yielded (100)/(002) reflections in XRD and the characteristic Raman modes, indicating an ordered graphitic structure suitable for future film deposition. The results confirm that the photoelectrochemical performance of each material critically depends on the balance between crystalline order and defect density. Based on this, strategic guidelines were established for material coupling: employing moderately reduced WO??? (6-8 sccm O? or 60% and 90% of P thermally treated under argon), depositing g-C?N? at 550?°C onto WO???. Although the heterostructure has not yet been completed, this study defines optimal synthesis windows and interfacial requirements that support subsequent stages toward the development of more efficient, stable, and economically viable composite photoelectrodes for the direct conversion of solar energy into green hydrogen.