This study was aimed at comparing the chemical structure of two rich premixed flames Ted respectively with a neat fuel:n-decane and a multi-component fuel, kerosene. Both flames were stabilized on a flat-flame burner at atmospheric pressure. Samples were withdrawn along the symmetry axis with a quartz microprobe and analyzed by gas phase chromatography. The main objective was to justify, for a future modelling purpose, the use of a detailed reaction mechanism validated in then-decane flame to predict the chemical structure of a kerosene flame. A close similitude was observed for the mole fraction profiles of both major species and main intermediates measured in each flame. Relative concentrations of the intermediate species in then-decane flame can be interpreted qualitatively by β-scission of large alkyl radicals.