In the paper, we proposed an evolution process of polyvinylidene fluoride (PVDF) macromolecular aggregation in a mixed solvent through the simple and slow gelation process at room temperature. The mixed solvent is prepared with a room-temperature solvent and a high-temperature solvent. The evolution process can be terminated by quenching and exchanging with nonsolvent in a nonsolvent coagulation bath properly, and then the vivid petal-like nanostructure and microspherulite is formed simultaneously. This hierarchical morphology endows PVDF with superhydrophobic and self-cleaning properties, which is useful to PVDF coating and membrane materials. The evolution processes are investigated through the measurements of differential scanning calorimetry (DSC), X-ray diffraction (XRD). In addition, the rheological properties of solution, dry gel and wet gel, are explored.