Mountain transition zones are highly sensitive to environmental change, yet the nonlinear coupling between topography and hydroclimate in controlling vegetation Net Primary Productivity (NPP) remains insufficiently constrained. Here, we reconstructed a 2003–2025 annual NPP time series for the West Qinling Mountains using a Carnegie–Ames–Stanford Approach (CASA)-based workflow that integrated Moderate Resolution Imaging Spectroradiometer (MODIS) vegetation products, fifth-generation European Centre for Medium-Range Weather Forecasts reanalysis for land (ERA5-Land) meteorological data, Shuttle Radar Topography Mission (SRTM) topography, and an Aridity Index (AI) dataset. Product-based validation against the annual MOD17A3HGF dataset indicated strong agreement, with a 23-year mean spatial Spearman correlation of 0.823 and a mean annual Pearson correlation of 0.773. The reconstructed dataset showed that 98.50% of the study area experienced increasing NPP, including 50.26% with significant increases, and the domain-wide mean Sen slope reached approximately 3.08 g C m⁻² yr⁻¹. Factor detection further showed that radiation (q = 0.253), elevation (q = 0.252), and temperature (q = 0.249) were the dominant single controls, whereas Aridity–Temperature (q = 0.367) and Elevation–Aridity (q = 0.367) represented the strongest interactions. The concentration of the strongest gains in gentle-slope and moderate-aridity settings suggests that vegetation recovery is maximized where topographic buffering and water-energy balance are jointly optimized. These results strengthen the interpretation of NPP dynamics in mountainous climate-transition environments and provide a basis for spatially targeted ecological restoration, regional carbon-budget assessment, and climate adaptation planning.