The cotton cellulose nanofibers framework of Z-Scheme ZnO/Ag3PO4 heterojunction has been successfully fabricated by a simple route of the electrospun-hydrothermal method. The photocatalytic activity of the as-prepared cotton cellulose nanofibers framework of Z-Scheme ZnO/Ag3PO4 heterojunction exhibits significant enhancement after the Ag3PO4 being introduced by the degradation of methylene blue (MB) under visible light irradiation. Furthermore, the high dispersibility of the CCNFs, high visible light absorption and photon-generated carriers separation of Z-Scheme ZnO/Ag3PO4 heterostructure are considered as the main reasons for the enhancement.