We report a One-step method to fabricate necklace-like Structures from zero-dimensional materials via electrospinning. PVA was used as polymer matrix for accomplishing necklace-like arrays of silica particles. We systemically investigated how the diameter of SiO2 particles, the weight ratio of PVA to SiO2, the voltage, and the relative content of PVA/SiO2/H2O influenced the morphology of electrospun fibers. SiO2 particles with diameter of 143 run tended to aggregate into bunches in the fibers, while 265 and 910 nm SiO2 particles tended to align along the Fibers one by one, resembling necklaces. The content of water in the PVA/SiO2/H2O solution showed critical influence on the diameter of fibers and consequently determined the morphology. Too thin solutions gave birth to blackberry-like structure; too condensed solution was too hard to eject from the orifice of the needle; when the ingredient was elaborately tailored, we obtained necklace-like structures. We believe that these results call serve as references to generating other complex structures involving polymers and particles via electrospinning and that these structures will be potentially useful in photoelectric devices, drug release, and optical components.