A straightforward, photocatalyst-free synthesis of 2-hydroxy-benzo[b]thiophen-3(2H)-ones is described. The obtained compounds represent analogs of the biologically active natural product thiacremonone with an extended ring system. The proposed method utilizes a photoinduced 1,6-hydrogen atom transfer (1,6-HAT) in 2-mercaptobenzaldehyde derivatives, enabling efficient cyclization under mild conditions. The utility of this method is demonstrated by the preparation of 16 novel analogs with high efficiency.