Primary unsaturated stibines ethenylstibine (1a), E-prop-1-enylstibine (Ib), ethynylstibine (2a), and prop-1-ynylstibine (2b) are synthesized by reaction of antimony trichloride with the corresponding vinyltributylstannanes 3a,b and alkynyltributylstannanes 4a,b, respectively, followed by a chemoselective reduction of the formed dichlorostibines 5a,b and 6a,b. Compounds 1a,b and 2a,b are characterized on the basis of spectral data (NMR, photoelectron spectroscopy and high resolution mass spectrometry). In particular, the PE spectra display very well-resolved bands (1a, 9.3, 10.3, 11.2, 11.9, 13.7. and 15.0 eV; 2a. 9.7, 10.5, and 11.2 eV). The alpha-unsaturated stibines exhibit a low stability at room temperature even in the presence of a solvent (tau(1/2) ca. 1 h) and lead to the formation of oligomeric material or an antimony mirror on the wall of the flask. Attempts to detect C-Sb multiple bond derivatives by a base-catalyzed rearrangement of 1 or 2 were unsuccessful.