Entanglement purification is to distill high-quality entangled states from low-quality entangled states. It is a key step in quantum repeaters, determines the efficiency and communication rates of quantum communication protocols, and is hence of central importance in long-distance communications and quantum networks. In this work, we report the first experimental demonstration of deterministic entanglement purification using polarization and spatial mode hyperentanglement. After purification, the fidelity of polarization entanglement arises from 0.268±0.002 to 0.989±0.001. Assisted with robust spatial mode entanglement, the total purification efficiency can be estimated as 109 times that of the entanglement purification protocols using two copies of entangled states when one uses the spontaneous parametric down-conversion sources. Our work may have the potential to be implemented as a part of full repeater protocols.