Natural and synthetic purine derivatives such as caffeine, theophylline, 6-mercaptopurine and 8-chlorotheophylline are important drugs. Due to the structural similarity of these compounds, it is intrinsically difficult to prepare chemosensors for their selective optical detection. Here, we describe a sensor array which can be used to differentiate pharmacologically important purine derivatives with good accuracy. The array is composed of four polysufonated fluorescent dyes, all of which can bind purines via π-stacking interactions. The complexation of the analytes results in partial quenching of the fluorescence. The fluorescence response of the four dyes provides a characteristic signal pattern, enabling the identification of thirteen purine derivatives at low millimolar concentration. Furthermore, it is possible to use the array for obtaining information about the quantity and purity of purine samples.