Abstract: Samples of blue ink taken from 110 ball pens of different brands and origins of production were analyzed and discriminated by GC-MS and TLC. The ink samples were divided into 6 categories based on the results of composition of solvents obtained by GC-MS. Compositions of dyes of the ink were studied by TLC. Based on the number of sample spots, their locations and colors, as well as the location of standard peak among the absorption peaks obtained after TLC scanning, the ink samples were divided into 17 categories. As a results of comprehensive study of the data of GC-MS and TLC, and considering the differences in compositions of the solvents and dyes, ink samples of the 110 ball pens were divided into 35 categories. More accurately, precise and systematic differentiation and recognition of the blue ink in a certain brand of ball pens was obtained as compared with the result of classification obtained by a single testing method.