Thirteen "legal highs" were purchased in different "smart shops" in the area of Lisbon, Portugal, during the month of February 2013. The samples were analyzed by a battery of analytical methods including Fourier transform infra-red (FTIR), gas chromatography coupled with mass spectrometry (GC-MS), proton nuclear magnetic resonance ((1)H NMR) and wavelength dispersive X-ray fluorescence (WD-XRF). Active ingredients were found either as single component or in mixtures in the different products. The cathinone derivative methedrone was present in three products; it is suspected to have a particular high toxicity and narrow therapeutic window linked with the methoxy group. A total of seven compounds were identified: 4-fluoromethcathinone, ethcathinone, buphedrone, methedrone, pentedrone, 3,4-dimethylmethcathinone and 4-methylethcathinone. Analytical profiles of all the samples were obtained and compared. Elemental composition of the products was obtained by XRF analysis. The inorganic profiles obtained contain useful information and can be used to distinguish and classify samples according to their origin.