As biomaterials with excellent biocompatibility, biodegradation and low toxicity, poly(ε-caprolactone) (PCL) and poly(lactic-co-glycolic acid) (PLGA) are widely applied as wound dressing and surgical suture in biomedical field. In this paper, an oblique section free surface eletrospinning (OSFSE) apparatus was utilized to prepare high-quality and high-output ZnO/PLGA/PCL nanofiber membranes (NFMs) for antibacterial materials. The effects of the weight ratio of PLGA and PCL on the viscosity and conductivity of electrospinning solutions as well as the yield, morphology and wettability of PLGA/PCL NFMs were researched, and the optimal weight ratio of 6:4 was determined. Then the effects of ZnO contents on the electrospinning solution properties as well as the yield, morphology, structure, wettability, mechanical property and antibacterial performance of ZnO/PLGA/PCL NFMs with the optimal ratio of PLGA and PCL were studied. The results indicated that the addition of ZnO could improve significantly the antibacterial effect of NFMs, and the NFMs with 3 wt% ZnO had excellent antibacterial activity against E. coli (95.3%) and S. aureus (95.7%).