Terrestrial vegetation is a substantial carbon sink and plays a foundational role in regional and global climate change mitigation strategies. The state of California, USA, commits to achieving carbon neutrality by 2045 in part by managing terrestrial ecosystems to sequester more than 80 MMT of CO2. We used a 35-year remotely sensed net primary productivity (NPP) product with gridded climate, soil, topography, and vegetation data to evaluate spatiotemporal drivers of NPP variation and identify drivers of NPP response to extremes in water availability within and among California’s major grassland, shrubland, and woodland ecosystems. We used generalized boosted models and linear mixed effects models to identify influential predictors of NPP and characterize their relationships with NPP across seven major vegetation cover types. Climate seasonality, specifically greater precipitation and warmer minimum temperatures in early spring and winter, was associated with greater NPP across space, particularly in chaparral, blue oak, and grassland systems. Temporal variation in maximum annual temperature and climatic water deficit showed a negative relationship with temporal variation in NPP in most vegetation cover types, particularly chapparal and coastal scrub. We found a significant decrease in NPP over time in most vegetation types, appearing to coincide with California’s recent mega-drought. However, response to water availability extremes differed by vegetation type. Grasslands, for example, showed a pronounced ability to upregulate NPP in extreme wet years while maintaining relatively high baseline NPP in extreme dry years. Our analysis characterizes several climate risks and conservation opportunities in using California’s natural lands to store carbon. Namely, shifts in climate seasonality and water availability extremes present risks to the ability of most of these systems to fix carbon, yet hotspots of NPP resilience may exist and could be enhanced through conservation and restoration. Additional mechanistic work can help illuminate these opportunities and prioritize conservation decision making.