Pure (+)-methyl epijasmonate was isolated from lemon ( Citrus limon Burm.) for the first time. To that aim, two commercial essential oils and one homemade extract were included in the present paper. First, a study on the appropriate chromatographic conditions to avoid the epimerization from methyl epijasmonate to the more stable methyl jasmonate was accomplished. The results obtained are discussed. The presence of (+)-methyl epijasmonate in the three samples studied was initially established through the direct injection into GC-MS. However, the overlapping of (+)-methyl epijasmonate with other matrix components made it necessary to employ a multidimensional technique. RPLC-GC analysis via through-oven transfer adsorption-desorption (TOTAD) provided the selectivity and sensitivity required, reflecting that the homemade lemon extract was an adequate natural source to obtain pure (+)-methyl epijasmonate by means of the collection of the corresponding RPLC fraction.