Polyvinyl alcohol (PVA) electrospun nanofibers (NFs) are ideal carriers for loading silver nanoparticles (Ag NPs) serving as antibacterial materials. However, it is still a challenge to adjust the particles size, distribution, and loading density via a convenient and facile method in order to obtain tunable structure and antimicrobial activities. In this study, Ag NPs surface decorated PVA composite nanofibers (Ag/PVA CNFs) were fabricated by the solvothermal method in ethylene glycol, which plays the roles of both reductant and solvent. The morphology and structure of the as-fabricated Ag/PVA CNFs were characterized by scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, X-ray diffraction, UV-visible spectroscopy, and Fourier transform infrared spectroscopy. Ag NPs had an average diameter of 30 nm, the narrowest size distribution and the highest loading density were successfully decorated on the surfaces of PVA NFs, at the AgNO3 concentration of 0.066 mol/L. The antibacterial properties were evaluated by the methods of absorption, turbidity, and growth curves. The as-fabricated Ag/PVA hybrid CNFs exhibit excellent antimicrobial activities with antibacterial rates over 98%, especially for the sample prepared with AgNO3 concentration of 0.066 mol/L. Meanwhile, the antibacterial effects are more significant in the Gram-positive bacteria of Staphylococcus aureus (S. aureus) than the Gram-negative bacteria of Escherichia coli (E. coli), since PVA is more susceptive to S. aureus. In summary, the most important contribution of this paper is the discovery that the particles size, distribution, and loading density of Ag NPs on PVA NFs can be easily controlled by adjusting AgNO3 concentrations, which has a significant impact on the antibacterial activities of Ag/PVA CNFs.