Sensor array is a new method used in aroma analysis. This technique was employed for the differentiation of 49 pure Valencia orange juices from 5 different origins representative of the main culture areas of citrus according to their volatile organic fractions. An experimental design was used to set analytical factors, which control the generation of the static headspace; therefore, the preliminary optimization of analytical conditions allows the evaluation of the potential of such an apparatus in this kind of survey. Results obtained were then statistically treated by multivariate analyses such as principal component analysis and factorial discriminant analysis. Sensor arrays performed a good discrimination of the whole juices in classing them according to the origin of Valencia oranges used. A calibration of the sensors was then performed to build a database aiming to classify the juices according to the origin of oranges involved. New supplementary samples were then analyzed to assess the efficiency of the database. This technique coupled with other ones such as high-pressure liquid chromatography and gas chromatography may be a new tool for the investigation of adulteration detection due to the authentication of the origin of raw materials employed in the orange juice processes.