The synthesis and characterization of ethyl{2‐[(phenylamino)methyl]phenoxy}zinc (1) and ethyl{2‐[(propan‐2‐ylideneamino)methyl]phenylamido}zinc (2) are reported. The phenoxide 1 was prepared starting from 2‐(phenylaminomethyl)phenol and diethylzinc and the phenylamide 2 was obtained from 2,2‐dimethyl‐1,2,3,4‐tetrahydroquinazoline and diethylzinc. The compounds were characterized by NMR spectroscopy (1H, 13C{1H}), IR spectroscopy, elemental analysis, TGA measurements, and X‐ray structure analysis. In the solid state both compounds form dimers where (1)2·4thf shows a planar Zn2O2 and (2)2 a planar Zn2N2 unit. Noteworthy, the aminal ring of 2,2‐dimethyl‐1,2,3,4‐tetrahydroquinazoline was opened by its reaction with diethylzinc to give an ylidene moiety at the benzylic nitrogen atom.