A nickel-catalyzed tandem reaction involving cyclic esterification/C–S bond formation has been developed. Starting from samples containing 3-(2-hydroxy-phenyl)-acrylic acids with 2-halide-benzenethiols, versatile biologically active 5-oxa-11-thia-benzofluoren-6-one compounds were efficiently synthesized in good to high yields. This new methodology provides an economical approach toward C–S bond formation.