This study investigated the inter-annual variations, transport pathways, pollution sources, and health implications of volatile organic compounds (VOCs) in Zhengzhou, China, a city notably affected by ground-level ozone (O3) pollution. Analyzing VOCs data from the summers of 2017–2021 revealed an average summer VOCs concentration of 61.8 ± 18.2 μg/m3, predominantly consisting of alkanes (55.0%), aromatics (22.5%), and alkenes (16.9%). The study identified significant year-to-year disparities in VOC abundances and compositions, which were closely linked to meteorological conditions, including temperature, wind speed, and relative humidity. Additionally, factors like air mass origin, direction and transport distance critically influenced the VOCs characteristics, with local air masses exhibiting higher VOC concentrations than those from distances of 100–500 km to the northwest, west and east. Positive Matrix Factorization (PMF) analysis identified major sources of VOCs as vehicle exhaust, oil and gas evaporation, solvent use, and biogenic emissions, with their contributions varying annually influenced by regional transport, environmental policies, and the COVID-19 pandemic. Health risk assessments, following U.S. Environmental Protection Agency guidelines, indicated negligible non-carcinogenic and carcinogenic risks from VOCs exposure, except for a potential carcinogenic risk from ethylbenzene. Solvent use sources were found to have the highest risks, with non-carcinogenic risks at 4.1 × 10−3 (negligible) and carcinogenic risks at 7.8 × 10−7 (with potentially carcinogenic in 2017 but negligible in subsequent years). This research underscored the complex dynamics of VOCs pollution and provided insights for developing effective pollution control strategies and enhancing public health in urban settings.