The transition to electric vehicles is projected to have considerable public health co-benefits, but most evidence regarding air quality and health impacts comes from projections rather than real-world data. We evaluated whether population-level respiratory health and air quality co-benefits were already detectable at the relatively low levels of zero-emissions vehicles (ZEVs: battery electric, plug-in hybrid, hydrogen fuel cell vehicle) adoption in California, and evaluated the ZEV adoption gap in underserved communities. We conducted a zip code-level ecologic study relating changes in annual number of ZEVs (nZEV) per 1000 population from 2013 to 2019 to: (i) annual average monitored nitrogen dioxide (NO₂) concentrations and (ii) annual age-adjusted asthma-related emergency department (ED) visit rates, while considering educational attainment. The average nZEV increased from 1.4 per 1000 population in 2013 (standard deviation [SD]: 2.1) to 14.7 per 1000 in 2019 (SD: 14.7). ZEV adoption was considerably slower in zip codes with lower educational attainment (p < 0.0001). A within-zip code increase of 20 ZEVs per 1000 was associated with a - 0.41 ppb change in annual average NO₂ (95 % confidence interval [CI]:-1.12, 0.29) in an adjusted model. A within-zip code increase of 20 ZEVs per 1000 population was associated with a 3.2 % decrease in annual age-adjusted rate of asthma-related ED visits (95 % CI:-5.4, -0.9). Findings were supported by a variety of sensitivity analyses. Observational data on the early phase ZEV transition in California provided a natural experiment, enabling us to document the first real-world associations between increasing nZEV and changes in air quality and health. Results suggest co-benefits of the early-phase transition to ZEVs but with an adoption gap among populations with lower socioeconomic status which threatens the equitable distribution of possible co-benefits.