The CALIOPE project, funded by the Spanish Ministry of the Environment, aims at establishing an air quality forecasting system for Spain. With this goal, CALIOPE modeling system was developed and applied with high resolution (4 km × 4 km, 1 h) using the HERMES emission model (including emissions of resuspended particles from paved roads) specifically built up for Spain. The present study provides an evaluation and the assessment of the modeling system, coupling WRF-ARW/HERMES/CMAQ/BSC-DREAM8b for a full-year simulation in 2004 over Spain. The evaluation focuses on the capability of the model to reproduce the temporal and spatial distribution of gas phase species (NO2, O3, and SO2) and particulate matter (PM10) against ground-based measurements from the Spanish air quality monitoring network. The evaluation of the modeling results on an hourly basis shows a strong dependency of the performance of the model on the type of environment (urban, suburban and rural) and the dominant emission sources (traffic, industrial, and background). The O3 chemistry is best represented in summer, when mean hourly variability and high peaks are generally well reproduced. The mean normalized error and bias meet the recommendations proposed by the United States Environmental Protection Agency (US-EPA) and the European regulations. Modeled O3 shows higher performance for urban than for rural stations, especially at traffic stations in large cities, since stations influenced by traffic emissions (i.e., high-NOx environments) are better characterized with a more pronounced daily variability. NOx/O3 chemistry is better represented under non-limited-NO2 regimes. SO2 is mainly produced from isolated point sources (power generation and transformation industries) which generate large plumes of high SO2 concentration affecting the air quality on a local to national scale where the meteorological pattern is crucial. The contribution of mineral dust from the Sahara desert through the BSC-DREAM8b model helps to satisfactorily reproduce episodic high PM10 concentration peaks at background stations. The model assessment indicates that one of the main air quality-related problems in Spain is the high level of O3. A quarter of the Iberian Peninsula shows more than 30 days exceeding the value 120 μg m−3 for the maximum 8-h O3 concentration as a consequence of the transport of O3 precursors downwind to/from the Madrid and Barcelona metropolitan areas, and industrial areas and cities in the Mediterranean coast.