This work involves the preparation of some new azo and azo-Schiff compounds derived from benzothiophene, dibenzothiophene, and diamines (1, 5-diaminonaphthalene, and thiocarbohydrazide). Azo compounds of benzothiophene and dibenzothiophene have been prepared using different solvents to enhance the miscibility of the polar aqueous solution of the diazonium salt and the slightly polar benzothiophene and dibenzothiophene. The Schiff's bases have been synthesized by the condensation reaction of carbonyl compound with the diamines. FT-IR has been used to identify the prepared compounds, whereas 1 H-NMR and 13 C-NMR were used to identify some others.