The CALIOPE-EU high-resolution air quality modeling system, namely WRF-ARW/HERMES-EMEP/CMAQ/BSC-DREAM8b, is developed and applied to Europe (12 km × 12 km, 1 h). The model performances are tested in terms of air quality levels and dynamics reproducibility on a yearly basis. The present work describes a quantitative evaluation of gas phase species (O3, NO2 and SO2) and particulate matter (PM2.5 and PM10) against ground-based measurements from the EMEP (European Monitoring and Evaluation Programme) network for the year 2004. The evaluation is based on statistics. Simulated O3 achieves satisfactory performances for both daily mean and daily maximum concentrations, especially in summer, with annual mean correlations of 0.66 and 0.69, respectively. Mean normalized errors are comprised within the recommendations proposed by the United States Environmental Protection Agency (US-EPA). The general trends and daily variations of primary pollutants (NO2 and SO2) are satisfactory. Daily mean concentrations of NO2 correlate well with observations (annual correlation r = 0.67) but tend to be underestimated. For SO2, mean concentrations are well simulated (mean bias = 0.5 μg m−3) with relatively high annual mean correlation (r = 0.60), although peaks are generally overestimated. The dynamics of PM2.5 and PM10 is well reproduced (0.49 < r < 0.62), but mean concentrations remain systematically underestimated. Deficiencies in particulate matter source characterization are discussed. Also, the spatially distributed statistics and the general patterns for each pollutant over Europe are examined. The model performances are compared with other European studies. While O3 statistics generally remain lower than those obtained by the other considered studies, statistics for NO2, SO2, PM2.5 and PM10 present higher scores than most models.