Abstract: In this work; a critical review about on-line gaseous phases generation with Fourier transform infrared (FTIR) spectrometry detection is presented. In this sense, different experimental approaches for the determination of ethanol and carbonates in different samples, and for the simultaneous determination of benzene, toluene and methyl tert-butyl ether in gasoline; and butyl acetate, toluene and methyl ethyl ketone in commercial paint solvents has been examined. In all these methods, the figures of merit are adequate for the proposed applications, and the results are in good agreement with those obtained by diverse reference procedures. Also, it is presented the recent development of the flow analysis-hydride generation-FTIR coupling for the individual and simultaneous determination of antimony, arsenic and tin, as well as some applications proposed for this technique. All this procedures are focused to demonstrate the real analytic potentiality depicted by the on line gaseous phase generation-FTIR spectrometry technique for the analysis of real samples.