It is well known that small substituted aromatic amines lose their substituents after electron ionization in a multistep fragmentation mechanism. In this contribution, the fragmentation reactions of N,N-diethyl-aniline and different methyl-substituted N,N-diethyl-methyl-aniline isomers are investigated with respect to the position of the methyl group attached to the aromatic ring system. Metastable ion decay reveals a complicated fragmentation mechanism leading to an interplay of the aromatic methyl group and the ethyl substituents at the amine function. A small change in the substitution leads to a significant change of the observed fragments indicating a participation of o-methyl groups in the fragmentation mechanism of the diethyl amino side chain. Because the underlying mechanisms are not fully understood, the presented investigations deliver through 13C isotopic labeling a deep insight into the hidden rearrangement and fragmentation mechanisms in these compounds.