Superhydrophobic surface with high solid/liquid adhesion is of great fundamental and technological importance. However, the fabrication of adhesive superhydrophobic polymer surfaces with high stability is rare, which limits the utilization of such surfaces in harsh environments. This paper illustrates a simple electrospinning way to produce fluorinated polyimide nanofibric mat with adhesive superhydrophobicity as well as high thermal stability. The water contact angle on the mat reaches as high as 157.8° and the adhesive force to a water drop is up to 98.3 μN. Moreover, the adhesive superhydrophobic polyimide mat is able to stand extreme heat up to 300 °C. By virtue of the facile electrospinning technique, large-area flexible mats can be easily achieved. Such an electrospun fluorinated polyimide mat will possess broader applications than ordinary organic superhydrophobic surfaces owing to its excellent stability in harsh environments.