The rapid proliferation of hybrid work models has radically altered organizational dynamics, dismantling traditional temporal and spatial boundaries between personal and professional spheres. While hailed for offering flexibility and autonomy, the hybrid framework has introduced complex psychological vulnerabilities, most notably digital burnout and technostress. This paper empirically investigates the determinants of digital burnout within hybrid work environments, focusing on the mediating role of constant connectivity urgency and the moderating influence of organizational psychological safety. Utilizing a cross-sectional quantitative design, data were collected from 420 knowledge workers across diverse professional service sectors. Structural equation modeling (SEM) revealed that blurred work-life boundaries and asymmetric digital monitoring significantly escalate technostress and consequent digital burnout. Crucially, the findings demonstrate that while individual resilience is insufficient to combat systemic digital fatigue, high organizational psychological safety profoundly buffers the negative impacts of constant connectivity. The study concludes by offering an empirical framework for sustainable hybrid work architectures, emphasizing the structural institutionalization of the 'right to disconnect' and a paradigm shift from synchronous surveillance to asynchronous output-based evaluation.