Multivariate techniques have been applied to the set of data obtained after one year sampling of volatile organic compounds (VOCs), including volatile aldehydes in the area of Madrid in order to evaluate the possible correspondence among groups of analysed compounds, as far as modelling of different emission sources in relation to location and season. The measurements were carried out at four sites in Madrid, characteristic for urban and suburban areas. Additionally, as reference, a rural area 100 km far from the city was considered. Results of correlation analysis, factor and cluster analysis are presented. Higher correlations were found between variables related with traffic emissions. Factor analysis results showed two main significant variables related to anthropogenic and biogenic emissions respectively. In relation to cluster analysis, samples were grouped according to sampling site and seasonal variations.