Earth Observation (EO) technology provides a unique means of obtaining information on land use/cover and of its changes, which is of key importance in many scientific and practical applications. Such data is already widely used, for example, in environmental practices or decision making related to food availability and security. As such, it is imperative to examine the suitability of different EO datasets for this purpose, including their synergies. Through a case study focusing on Wales, this work aims at exploring the added value of the synergistic use of Optical and Radar data (from the Landsat TM and ASAR sensors respectively), towards improving the accuracy of land cover classifications from EO datasets. Two classificationsone based on optical data alone and another one developed from the synergy of optical and RADAR datasets acquired nearly concurrently were developed for the studied region. Evaluation of the derived land cover maps was performed on the basis of the confusion matrix using validation points derived from a Phase 1 Habitat map of Wales. In addition, McNemar's test was implemented to assess the statistical significance of the obtained results. The results showed statistically significant evidence that the use of optical data synergistically with the radar data provides more accurate land cover maps in comparison with the use of optical data alone.