This invention provided a preparation method of the composite which was immobilized Paracoccus denitrificans on modified graphene oxide and its application. The composite was obtained by following the steps below: 1) Synthesis of graphene oxide; 2) Synthesis of modified graphene oxide; 3) Acclimatization and immobilization of Paracoccus denitrificans. In this invention, the raw materials were low-cost and easily obtained used in the preparation process; easy operation, convenient, and no expensive instruments during the whole process; this invention of the composite could remove DMF from wastewater completely, and with the advantages of high efficiency, good recycle performance, economical, environmentally friendly, better feasibility.