Polyhalogenated-2-nitro-1, 3-butadienes are important synthetic precursors for a variety of poly-functionalized bioactive heterocycles. Herein, we report the reactions of 1, 1, 3, 4, 4-pentachloro-2-nitro-1, 3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to obtain highly functionalized (E)-polyhalodiene-2-nitro-1, 3-butadiene derivatives. Most of these reactions were found to be highly selective resulting in good to high yields of the products. All new compounds have been characterized by nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and Fourier transform infrared spectroscopy (FT-IR) spectroscopic data. Single crystal X-ray structure analysis of compound 8c is reported.