The ventilative sole structure includes a sole, a first one-way valve, and a second one-way valve. The sole's heel portion includes a hollow chamber inside and a bottom piece beneath the chamber. The first one-way valve is configured on a circumferential wall of the chamber. The second one-way valve is configured between a tread portion of the sole and the chamber. When a user wears a shoe with the ventilative sole structure, air enters the chamber through the first one-way valve when the user raises his/her feet, and air is released from the chamber through the second one-way valve towards the tread portion when the user treads on the ground and compresses the chamber, thereby enhancing ventilation and removing odor of the shoe.