The lack of single crystalline Ti3SiC2 samples is currently limiting the accurate measurement of its basic properties as its layered crystalline structure presents a very strong anisotropy. In this letter, we report the growth of pure Ti3SiC2 single crystals after a careful study of the Ti3SiC2 liquidus surface extent through thermodynamical calculations. From a Raman scattering study on those single crystals, an unambiguous assignment of most of the phonon modes has been established, giving an answer to the discrepancies existing in the literature. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3558919]