Starting from 6-amino-6-methylpentafulvene (2) “ortho”-C-acylation or N-acylation can be achieved selectively. Treatment of 2 with phthaloyl-protected amino acid chlorides derived from alanine (3a) or valine (3b) leads exclusively to the formation of the “ortho”-C-acylated derivatives 4, isolated as racemates. Optically active N-acylated products 7 were prepared by coupling 5, obtained by NH deprotonation of 2, with the 1-hydroxybenzotriazole (HOBt) active-esters of alanine (6a), valine (6b), or leucine (6c) bearing benzylprotected amino groups. Complexes 2, 4a, 4b, and 7a were characterized by X-ray diffraction. Electron-withdrawing groups attached at the “ortho” ring position lead to a shortening of the external C6−N bond, whereas electron-withdrawing groups bound to the nitrogen atom lead to an elongation of the C6−N bond, compared to the parent system 2.