The previously established aluminium-chloride-(AlCl 3 )-catalysed electrophilic aromatic substitution (EAS) of benzene (PhH) with thionyl chloride (SOCl 2 ) has been extended to toluene (PhCH 3 ), chlorobenzene (PhCl), and phenol (PhOH). -CH 3 was found to be mainly a para-director with a minor ortho-directing effect on the EAS reactions giving diaryl sulfoxides (Ar 2 SO). -Cl was found to be exclusively a para-director for formation of Ar 2 SO. All the -CH 3 , -Cl, and -OH groups were shown to be exclusive para-directors for formation of diaryl sulfides (Ar 2 S) from the EAS reactions. Although the reactions of PhH and PhCH 3 with SOCl 2 in the presence of AlCl 3 gave the major Ar 2 SO and minor Ar 2 S at ambient temperature, the phenol (PhOH) reaction was shown to give only the reduced sulfide (p-HOC 6 H 4 ) 2 S with no sulfoxide (p-HOC 6 H 4 ) 2 SO formed. The mixed diaryl sulfoxides ArSOAr′ (Ar, Ar′=C 6 H 5 , p-CH 3 C 6 H 4 ; C 6 H 5 , o-CH 3 C 6 H 4 ; and C 6 H 5 , p-ClC 6 H 4 ) were produced in the AlCl 3 -catalysed reactions of SOCl 2 with molar 1:1 PhH-PhX mixtures (X=CH 3 and Cl). Efforts to enhance the yield of S-aryl arenesulfonothioates ArSO 2 SAr (Ar=Ph, p-CH 3 C 6 H 4 , and p-ClC 6 H 4 ) from the AlCl 3 -catalysed EAS reactions of SOCl 2 were made, showing that decreasing the molar ratios of ArH/SOCl 2 or lowering the temperature resulted in an increase in the product yield. A detailed mechanism has been proposed to account for the formation of ArSO 2 SAr. The Lewis-acid-MCl 3 -(M=Al and Fe)-catalysed EAS reactions of PhH with selenyl chloride (SeOCl 2 ) were demonstrated to give the reduced diphenyl selenide (Ph 2 Se) and diphenyl diselenide (PhSeSePh) via novel auto-redox processes in selenium of the key EAS intermediates.