In this paper, an easy-operational, high-yielding method for the gram-scale synthesis of 3-sulfonyl flavanones is described by a one-pot straightforward POCl3 mediated intermolecular (5 + 1) annulation of the β-ketosulfones with an o-hydroxyaryl group (dual nucleophile) and arylaldehydes (dual electrophile) in refluxing toluene for 3 h. A plausible mechanism is proposed and discussed. This protocol provides a highly effective annulation via one carbon-oxygen (C-O) and one carbon-carbon (C-C) bond formations.