Novel p-type NiO/n-type CeO2 heterojunctions, with cubic NiO particles embedded on the CeO2 nanofibers, were successfully prepared by the electrospinning technique. The photocatalytic activity for MB degradation under UV light irradiation of the NiO/CeO2 heterojunction is much higher than, that of pure NiO or CeO2. The rate constant of MB degradation by NiO/CeO2 is about 4 times and 2 times than those of pure NiO and CeO2 under UV light irradiation, respectively. The excellent photocatalytic activity of the NiO/CeO2 heterostructures is closely related to the fast transfer and efficient separation of electron-hole pairs between NiO and CeO2 due to the formation of the heterojunction and their matching band positions. (C) 2014 Elsevier B.V. All rights reserved.