Superhydrophobic surface with strong solid/liquid adhesion is considered to be of great fundamental and technological importance. However, the fabrication of adhesive superhydrophobic polymer surfaces with high thermal stability is rare, which limits the utilization of such surfaces in harsh environment. This paper illustrates a simple one-step electrospinning way to produce adhesive superhydrophobic surfaces with high thermal stability. A soluble fluorine-containing polyimide with proper water-repellency is designed and synthesized. Then it is electrospun into non-woven mat with highly nano porous surface structure. Water contact angle on the mats reaches as high as 157.8° and the adhesion of the mat to water measures up to 98.3 μN. And adhesive superhydrophobic polyimide mats are able to stand extreme heat up to 300°C. Moreover, adhesion of the mats to water can be tuned by the thermal treatment. In addition, by taking the advantage of the electrospinning technique, large-scale flexible mats can be easily achieved. Such electrospun polyimide mats have the potentials to be applied in harsh environment where heat or tension could take place.