Tropospheric ozone (O₃), a secondary pollutant of mounting global concern, emerges from complex, nonlinear photochemical reactions involving nitrogen oxides (NO_x) and volatile organic compounds (VOCs) under dynamically evolving meteorological conditions. Accurately characterizing and effectively regulating O₃ formation necessitates not only precise and multi-dimensional precursor observations but also modeling frameworks that are structurally coherent, chemically interpretable, and sensitive to regime variability. Despite significant technological progress, current research remains markedly fragmented: observational platforms often operate in isolation with limited vertical and spatial interoperability, while modeling paradigms—ranging from mechanistic chemical transport models (CTMs) to data-driven machine learning approaches—frequently trade interpretability for predictive performance and struggle to capture regime transitions across heterogeneous environments. This review provides a dual-perspective synthesis of recent advances and enduring challenges in the VOC–O₃ research landscape. We first establish a typology of ground-based, airborne, and satellite-based VOC monitoring systems, evaluating their capabilities, limitations, and roles within a vertically structured sensing architecture. We then examine the evolution of O₃ modeling strategies, from empirical and semi-mechanistic models to hybrid frameworks that integrate physical knowledge with algorithmic flexibility. By diagnosing the structural decoupling between observation and inference, we identify key methodological bottlenecks and advocate for a system-level redesign of the VOC–O₃ research paradigm. Finally, we propose a forward-looking framework for next-generation atmospheric governance—one that fuses cross-platform sensing, regime-aware modeling, and policy-relevant diagnostics into an integrated, adaptive, and chemically robust decision-support system.