A headphone ear cup for mounting on a surface of a speaker unit of a headphone includes an annular cushion having a sound hole at a center thereof, and a composite cover having a ventilative layer and an air-tight layer. The composite cover wraps around the annular cushion and defines an inner-side portion, an outer-side portion and an ear-abutting portion. The ventilative and air-tight layers are respectively formed by the outer-side portion and a composite of the inner-side and ear-abutting portions or by a composite of the outer-side and ear-abutting portions and the inner-side portion. Therefore, the ventilative layer and the annular cushion form a good heat dissipation path to have excellent air-permeable property, and air-tight layer provides an improved acoustic field effect.