The interaction of triammine(tricarbonyl)chromium with 1,3-benzodioxole or some its derivatives (2,2-dimethyl1,3-benzodioxole, 2-methyl-1,3-benzodioxole, 2-phenyl-1,3-benzodioxole) led to corresponding (eta 6-1,3-benzodioxole)tricarbonylchromium complexes. The novel compounds were characterized by NMR spectrometry and mass-spectroscopy. The performed single-crystal X-ray diffraction study confirmed the formation of complexes via eta(6)-coordination of 1,3-benzodioxole ligand by chromium atom. It was shown that in the case of 2-phenyl-1,3benzodioxole both benzodioxole or phenyl fragments may be coordinated by Cr(CO)(3) moiety. The performed calculations have shown the possibility of intramolecular eta 6- eta 6-haptotropic rearrangement. The antimicrobial activity of the obtained tricarbonylchromium complexes has been evaluated.