A novel exclusive β-selective O-aryl glycosylation was developed using glycosyl chloride and arylboronic acid with a palladium catalyst under an air atmosphere. The reaction was insensitive to moisture and characterized using readily available and bench-stable glycosyl chloride and arylboronic acid as substrates. A diverse range of substrate scopes, including various arylboronic acids and glycosyl chloride donors, was well-tolerated in this method. Arylboronic acid was oxidized by O2 in air to produce phenol as the aromatic source. This new strategy provides an alternative route and may find broad applications in efficient synthesis of bioactive O-aryl glycosides in the future.