Abstract Polymer nanofiber aerogels are highly flexible and elastic. However, their preparation in a simple, low‐cost, and environmentally friendly manner remains challenging. Herein, a green strategy for preparing an ultralight poly(vinyl alcohol) (PVA) nanofiber aerogel by electrospinning and freeze‐drying is reported. A simple thermal crosslinking method is used to make a mechanically robust material that can withstand up to 1000 times its own weight, i.e., no toxic crosslinking agents or organic solvents are used in any part of the fabrication process. The optimal aerogel has high porosity (99.1%), and consequently excellent thermal insulation performance and low thermal conductivity (0.033 W m −1 K −1 ). Furthermore, the flexibility and hierarchical micronano structure of the aerogel qualify it as a promising candidate for air filters and intelligent wearable sensors.