New opportunities for high-performance CMOS-compatible optoelectronic devices have accelerated the interest in vertically configured device topologies that enable next-generation photonic technologies. Lately, TiN has been identified as a promising refractory metal–ceramic for the hybrid integration of emerging semiconductor materials on a variety of substrates, including Si, MgO, and sapphire. Among these, Si is the least expensive and most commonly used element and substrate material in the semiconductor device industry. Following these examples, a hybrid oxide–nitride–Si stack is proposed and thoroughly investigated herein for its potential use in DUV optoelectronic device applications. The stack comprises β-Ga₂O₃ thin films grown heteroepitaxially on TiN/Si platforms, wherein the TiN interlayers were heteroepitaxially grown on bulk (100)-oriented Si and act as lattice-mismatched templates and bottom device electrodes. Albeit the relatively large lattice mismatch between Si and TiN, a low in-plane rotation of 3 ∘ revealed that the TiN layers continued to grow as a bulk crystal, paving the way for heteroepitaxial β-Ga₂O₃ thin films being grown without exhibiting amorphous and metastable phases. DUV photodetectors based on this optoelectronic heterostructure exhibited average peak spectral responsivity and external quantum efficiency levels as high as 249 A/W and 1.23 × 10⁵%, respectively, in the ultraviolet-C regime at an illuminating power density of around 12 µW/cm².