The first examples of 1-stibaphenalenes 1 and 6 have been prepared by the condensation of dibromophenylstibane with 1,5-dilithium intermediate 5, generated in situ from (Z)-1-bromo-2-[1-(8-bromonaphthyl)]-1-trimethylsilylethene (4). Single crystal X-ray analysis of 1 revealed that the naphthalene and the fused stibinine ring are almost coplanar (mean deviation 0.0264 Angstrom), and the phenyl group on the antimony is oriented perpendicular with the phenalene ring.