Here, we developed a new cobalt nanocatalyst supported on N–SiO2-doped activated carbon (Co/N–SiO2–AC), which exhibits excellent catalytic performance towards the oxidative esterification of (hetero)aryl and alkyl thiols with alcohols. A wide array of sulfinic esters were efficiently afforded in an exclusive chemoselective manner. The developed synthetic method proceeds with the merits of mild reaction