Electrospinning is an important way to prepare fibers. In this paper, hydrophobic and conductive composite fiber membranes were prepared by opposite electrospinning. The hydrophobic material was trimethylethoxysilane, the conductive material was graphene, and polyvinylpyrrolidone was introduced as the carrier material of graphene. It was found that the sol-gel time, the content of silane coupling agent and low-temperature storage of the solution have a certain influence on the hydrophobicity and spinnability of the fiber membrane. At the same time, the effect of graphene content on the spinnability and the electrical conductivity of composite fiber membrane were studied. The results showed that the composite fiber membrane has good hydrophobic properties and electrical conductivity. The water contact angle of the fiber membrane reaches 139.6 degrees, and the conductivity reaches 1972.78 S cm(-1).