Abstract Atomic-scale control in plasma processing is becoming increasingly critical for fabricating of advanced semiconductor devices, particularly as the industry shifts toward three-dimensional (3D) architectures and high-aspect-ratio (HAR) structures. This review presents a comprehensive overview of recent developments in atomic-scale controlled plasma processes, organized along two key directions: the hierarchical structure of plasma–surface interactions and the generational evolution of atomic layer processing (ALP) technologies. We examined the gas phase, where molecular design enables selective generation of ions and radicals; the boundary layer, where transport phenomena govern species delivery into nanoscale features, and the surface, where temperature-dependent reactions and cyclic processing determine etching selectivity and precision. Building on this foundation, we outline five generations of ALP—from thermal atomic layer deposition to transport-aware, temporally and structurally decoupled processes—highlighting the increasing sophistication of process control. The review further explores the transition from empirical recipe development to science-based, data-driven methodologies. By integrating quantum-chemical modeling, advanced diagnostics, and machine learning, we demonstrated how predictive models can link plasma species composition to process outcomes, enabling autonomous and adaptive control strategies. Finally, this review discusses the broader societal implications of plasma process innovation through the E 4 quartet: energy and resource efficiency, environmental sustainability, evolutionary advancement, and educational promotion. These principles guide the development of sustainable and intelligent atomic-scale manufacturing technologies that are not only technically advanced but also socially responsible.