The chemical structures of thiophenol and its derivatives are analogous to phenols, where the oxygen atom in the hydroxyl group (-OH) bonded to the aromatic ring in phenol is replaced by a sulfur atom.

2 methods are the reduction of benzenesulfonyl chloride with zinc[5] and the action of elemental sulfur on phenyl magnesium halide or phenyllithium followed by acidification.

Via the Newman–Kwart rearrangement, phenols (1) can be converted to the thiophenols (5) by conversion to the O-aryl dialkylthiocarbamates (3), followed by heating to give the isomeric S-aryl derivative (4).

[6] In the Leuckart thiophenol reaction, the starting material is an aniline through the diazonium salt (ArN2X) and the xanthate (ArS(C=S)OR).

[7][8] Alternatively, sodium sulfide and triazenes can react in organic solutions and yield thiophenols.

[10] The reaction medium is corrosive and requires ceramic or similar reactor lining.