Surface marine sediments from Ría de Arousa estuary were analyzed for humic and fulvic acids by UV-visible spectrometry and have been characterized using elemental analysis (carbon, hydrogen and nitrogen elemental composition) and spectrometric data (A2/A4 ratio, absorbancies at 270 and 407 nm and E4/E6 ratio, absorbancies at 465 and 665 nm). These variables have been used as discriminating factors to distinguish of marine and terrestrial origin of humic and fulvic acids in Ría de Arousa surface marine sediments. Principal component analysis, PCA, and cluster analysis, CA, have been used as unsupervised pattern recognition procedures. The half-range central value transformation was used as data pre-treatment to homogenize data. After a Varimax rotation, PCA applied to humic acid data has reveled that spectrometric A2/A4 and E4/E6 ratios are the main dominating features in the first principal component (48.6% of total variance), the humic acid content is the feature with the highest weight in the second principal component (22.9% of the total variability) and the carbon elemental composition domain in the third principal component (13.3% of total variance). Results from PCA have revealed that surface sediments collected at inner-left part of the estuary and at the mouth of the river Ulla belong to the same group. Similarly, PCA has shown that surface sediments from the right mouth of the estuary form a compact group. Taking in account the water circulation in Ría de Arousa estuary, these findings mean that the organic matter in surface sediments from the inner-left part of the estuary derived mainly from terrestrial organic matter while the organic matter in surface sediments from the right mouth of the estuary is mainly derived from marine sources. Finally, it must be noticed that any classification of surface sediments was assessed when applying of PCA and CA from fulvic acids data.