<p>Air pollution control (APC) has emerged as a critical bottleneck for China’s sustainable development. Green technological innovation (GTI) and industrial structure transformation (IST) are widely regarded as pivotal drivers for improving environmental quality, yet their interactive mechanisms remain underexplored. Using panel data from 270 prefecture-level cities in China, this study constructs a comprehensive analytical framework to examine: (1) the direct effect of GTI on APC; (2) the mediating roles of industrial structure upgrading (TS) and industrial structure rationalization (TL) in the GTI–APC relationship; (3) the moderating effects of command-and-control environmental regulation (CER) and policy-oriented environmental regulation (PER); (4) heterogeneity between border and non-border areas; and (5) nonlinear threshold effects based on economic development and industrialization levels. The empirical results show that: (1) GTI significantly reduces fine particulate matter concentrations, confirming its direct pollution-control effect; (2) TS plays a significant mediating role in the GTI–APC relationship, whereas TL does not; (3) contrary to conventional expectations, CER weakens the emission-reduction effect of GTI, while PER strengthens it; (4) the pollution-reduction effect of GTI is more pronounced in border areas than in non-border areas; (5) nonlinear threshold effects exist: the positive impact of GTI intensifies with economic development and industrialization levels. Based on these findings, this study proposes targeted policy recommendations for differentiated environmental regulation, cross-regional coordination, and technology-enabled border pollution governance.</p>