The present research is focused on the GC-FID determination of fatty acid methyl esters (FAMEs) in diesel blends, by means of an ionic liquid stationary phase, characterized by a dicationic 1,9-di(3-vinyl-imidazolium)nonane bis(trifluoromethyl)sulfonylimidate structure (SLB-IL100). The high polarity of the ionic liquid stationary phase allowed the separation of the FAMEs, from the less-retained hydrocarbons, thus avoiding the requirement of a hydrocarbon LC pre-separation. The results derived from the analyses of a soybean FAMEs B20 sample, carried out on an SLB-IL100 conventional column (30 m x 0.25 mm i.d. x 0.20 mm d(f)), were compared with those attained on a polyethylene glycol column, of equivalent dimensions. Conventional and fast GC methods, for the analysis of FAMEs in diesel blends, were developed on an SLB-IL100 30 m x 0.25 mm i.d. x 0.20 microm d(f) and on an SLB-IL100 12 m x 0.10 mm i.d. x 0.08 microm d(f) column, respectively. The optimized IL methods were subjected to validation: retention time and peak area intra-day precision (n=5) were good, with CV % values lower than 0.08% and 4.9%, respectively. With regards to the quantitation of FAMEs in biodiesel blends, a five points calibration curve was constructed, using C(17:0) as internal standard.