Abstract The syntheses of naphtho[1,2–6:7,6‐ b ′]bisbenzo[ b ]thiophene ( 4 ), naphtho[1,2–6:7,8‐ b ′]bisbenzo[ b ]thiophene ( 5 ), naphtho[2,1‐ b :7,6‐ b ′]bisbenzo[ b ]thiophene ( 8 ), naphtho[2,1‐ b :7,8‐ b ′]bisbenzo[ b ]thiophene ( 9 ), naphtho‐[1,2–6:5,6‐ b ′]bisbenzo[ b ]thiophene ( 14 ), naphtho[1,2–6:6,5‐ b ]bisbenzo[ b ]thiophene ( 17 ) and naphtho[2,1–6:‐6,5‐ b ′]bisbenzo[ b ]thiophene ( 23 ) are reported.