This paper aims to provide scientific support for decision-making in the field of improving air quality by evaluating pollution reduction measures included in the current Spanish policy framework of the 1st National Air Pollution Control Programme (NAPCP). First, the health impacts of air quality are estimated by using the concentrations estimated by multiscale air quality modeling and the recommended concentration–response functions (CRF), specifically as a result of exposure to particulate matter (PM), nitrogen dioxide (NO2), and ozone (O3). Second, the associated external costs are calculated by monetization techniques. Two scenarios are analyzed: a package including existing measures (WM2030) and a package with additional measures (WAM2030). Compared with the baseline scenario, an improvement was found in the health effects of NO2, PM10, and PM2.5, while for O3 there was a slight worsening, mainly due to the increase in the O3 metric used (SOMO35), which increases over some urban areas. Despite this, the monetary valuation of the total effects on health as a whole shows external benefits due to the adoption of measures (WM2030), compared with the reference scenario (no measures) of more than € 17.5 billion and, when considering the additional measures (WAM2030), benefits of about € 58.1 billion.