Structural isomers of disubstituted benzenes are difficult to distinguish with most mass spectrometric methods. Consequently, conventional concepts for the distinction of isomers are based on coupling mass spectrometry with a chromatographic method. As an alternative approach, we propose the combination of femtosecond laser ionization with time-of-flight mass spectrometry (fs-LIMS). The possibility of systematic tailoring of fs-laser pulse shapes opens access to a multidimensional analytical technique capable of distinguishing structural isomers of the title molecules.